Use of multiple charged ionic compounds derived from polyamines for waste water clarification

ABSTRACT

Disclosed herein are the water clarification compositions and method of using the disclosed water clarification compositions for clarifying a water system or waste water source. Specifically, the disclosed compositions comprise and methods use multiple charged cationic or anionic compounds that are derived from polyamines through an aza-Michael addition with an activated olefin having an ionic group. The disclosed water clarification methods or compositions are found to be more effective than those methods or compositions including commonly used single quaternary compounds for reducing turbidity in water systems or waste water sources.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119 to provisionalapplication Ser. No. 62/724,360, filed Aug. 29, 2018, hereinincorporated by reference in its entirety.

This application also relates to U.S. application Ser. No. ______, filedsimultaneously herewith, which claims priority under 35 U.S.C. § 119 toprovisional application Ser. No. 62/724,398, filed on Aug. 29, 2018 andtitled “MULTIPLE CHARGED IONIC COMPOUNDS DERIVED FROM POLYAMINES ANDCOMPOSITIONS THEREOF AND USE THEREOF AS REVERSE EMULSION BREAKER IN OILAND GAS OPERERATIONS.” The entire contents of these patent applicationsare hereby expressly incorporated herein by reference including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof.

FIELD OF THE INVENTION

The present disclosure relates generally to the field of waste waterclarification. In particular, the present disclosure relates to using anew class of multiple charged cationic or anionic compounds that are thereaction products of an aza-Michael Addition reaction between polyaminesand activated olefins containing an ionic group for water clarification.The disclosed multiple charged cationic or anionic compounds or theirsalts have at least two cationic or anionic charges within eachmolecule. The disclosed compounds are useful as water clarificationagents for treating a water system or waste water source from food andbeverage, steel, automotive, transportation, refinery, pharmaceutical,metals, paper and pulp, chemical processing, and hydrocarbon processingindustries.

BACKGROUND OF THE INVENTION

During a water treatment process, it is often necessary to separatesolids/liquid or oils from water. Suspended solids or liquids/oils canbe removed from water by a variety of processes, includingsedimentation, straining, flotation, filtration, coagulation,flocculation, and emulsion breaking among others.

Water being treated for solids removal often has as little as severalparts per billion of suspended solids and/or dispersed oils or maycontain a lot of suspended solids and/or oils. Solids/liquid orliquid/liquid separation processes are designed to remove solids fromliquids, or liquids from liquids.

While strictly mechanical means have been used to effect solids/liquidor oil/water separation, modern methods often rely on mechanicalseparation techniques that are augmented by inorganic, syntheticpolymer, or natural polymeric materials to accelerate the rate at whichsolids, oils, or solids and oils can be removed from water. This processis generally refereed as water clarification. The chemicals used forwater clarification, such as inorganic, synthetic polymer, or naturalpolymeric materials are generally called water clarification agents.

Clarification generally refers to the removal of non-settleable materialby coagulation, flocculation, and sedimentation. Coagulation is theprocess of destabilization of the colloid by neutralization of thesurface charges of the colloid. Once neutralized, particles no longerrepel each other and can come together to form larger settleable solidsor oil droplets, which can then be removed from the water bygravitational settling or flotation. Coagulation is necessary forremoval of colloidal sized suspended matter.

Flocculation is the process of bringing together the destabilized,“coagulated” particles to form a larger agglomeration or floe forincreasing the solid-liquid separation process.

Examples of water clarification include the treatment of raw water withcationic coagulant polymers, to settle suspended particulates and makethe water usable for industrial or municipal purposes. Other examples ofthese processes include the removal of colored soluble species frompaper mill effluent wastes, use of organic flocculant polymers toflocculate industrial and municipal waste materials, sludge recovery,use of emulsion breaking and drainage aids in the manufacture of pulpand paper, and the use of flotation aids in mining processing.

The nature of the solids or oils to be removed and the mechanicalprocess usually determine choices of clarification agents. For example,it is conventional to utilize a dual chemical/polymer program forclarification of raw water in which an aluminum chemistry is commonlyused with an organic coagulant to remove soluble color and othercontaminants. When colloidal solids need to be removed from water sothat the biochemical oxygen demand, chemical oxygen demand, and totalsuspended solids being discharged to a receiving stream need to beminimized, a low molecular weight cationic coagulant followed by ahigher molecular weight flocculant are typically used.

Water containing emulsified oil can be difficult to treat by physicalprocesses alone. In such circumstances, demulsifying coagulants andflocculants can be used to break the emulsion and hasten agglomerationof the oil particles formed. Inorganic coagulants alone or incombination with organic polyelectrolytes have been used inde-emulsification.

However, the existing treatments are not completely satisfactory becausethey increase solids content, which can cause sludge disposal problemswith other coagulants/flocculants for clarifying oily waste water fromfood and beverage, steel, automotive, transportation, refinery,pharmaceutical, metals, paper and pulp, chemical processing, andhydrocarbon processing industries.

Also, in industries such as food and beverage (F&B) and their downstreamapplications, organic water clarification agents are preferred over theinorganic counterparts, despite the conventional outperformance ofinorganics compared to organic agents. For example, in F&B industries,sludge can be further used as pet feed or in land application, so theinorganic content must be maintained as low as possible. The other majordisadvantage with using inorganic chemistries is scaling, especially inindustries such as oil refineries. To mitigate these issues, effortshave been steered towards finding an equivalent organic replacement tothe current inorganic line of products, especially for oil removal in awaste water system.

For more effective and efficient water clarification process, variouschemicals as coagulant/flocculants were invented or investigated. Thesechemicals include various cationic polymers. However, bettercoagulant/flocculants are still needed because the existing ones arestill unsatisfactory for all applications.

Accordingly, it is an objective to develop novel water clarificationagents having improved water clarification properties.

It is a further objective of the disclosure to use the compoundsdisclosed herein in water clarification compositions, alone or incombination with other coagulant/flocculant agent(s) and other waterclarification composition agents, for water clarification and/or forremoving oil.

It is a further objective of the disclosure to use the compoundsdisclosed herein in water clarification compositions, in combinationwith inorganic agents, to provide a mechanism to decrease the overallusage of the inorganic agents.

These and other objects, advantages and features of the presentdisclosure will become apparent from the following specification takenin conjunction with the claims set forth herein.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein are methods of clarifying a water system using novelcompounds and water clarification compositions comprising the novelcompounds. Particularly, the disclosed methods use or compositionscomprise one or more multiple charged cationic compounds having two ormore positive charges or anionic compounds having two or negativecharges within a single molecule. These multiple charged ionic compoundsare of various molecule sizes, derived from water soluble polyamines,and are water soluble.

The exemplary multiple charged cationic compounds disclosed herein havesuperior performance than conventional coagulants for clarifying raw,process and waste waters. The exemplary multiple charged cationicdisclosed here also show improved performance when they are used as acoagulant for removing oil in a water source from food industry and oilrefinery industry.

An advantage of the methods and compositions disclosed herein is thatthe multiple charged cationic or anionic compounds used in the methodsor composition can be used as the sole treatment agent by usingdifferent polyamines or PEIs as starting material and different levelsof incorporating ionic groups and their performances are often muchbetter than the conventional coagulants.

In one aspect, disclosed herein is a water clarification composition,wherein the water clarification composition comprises a compound and oneor more additional water clarification composition agents, wherein thecompound is derived from an aza-Michael Addition Reaction between apolyamine (Michael donor) and an activated olefin (Michael acceptor)having an ionic group according to one of the following formulas

wherein X is NH or O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2′) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; m is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾, Y′ is —COOH, —SO₃H, —PO₃H,—OSO₃H, —OPO₃H, or a salt thereof; and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2 or more positive charges or multiple chargedanionic compound having 2 or more negative charges and wherein the waterclarification composition reduces turbidity of the water system.

In another aspect, disclosed here is a method of clarifying a watersystem, wherein the method comprises providing a water clarificationcomposition into a water system, wherein the water clarificationcomposition comprises a compound or its salt and one or more additionalwater clarification composition agents, wherein the compound is derivedfrom an aza-Michael Addition Reaction between a polyamine and anactivated olefin having an ionic group according to one of the followingformulas

wherein X is NH or O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2′) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H, —PO₃H,—OSO₃H, —OPO₃H, or a salt thereof, and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2 or more positive charges or multiple chargedanionic compound having 2 or more negative charges and wherein the waterclarification composition reduces turbidity of the water system.

The forgoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodimentsand features described above, further aspects, embodiments, and featuresof the present technology will become apparent to those skilled in theart from the following drawings and the detailed description, whichshows and describes illustrative embodiments of the present technology.Accordingly, the figures and detailed description are also to beregarded as illustrative in nature and not in any way limiting.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows an exemplary generic reaction scheme to produce a multiplecharged cationic compound by an aza-Michael addition reaction between alinear polyamine and an activated olefin (α, β-unsaturated carbonylcompound) containing cationic group.

FIG. 2 shows an exemplary generic reaction scheme to produce a multiplecharged cationic compound by an aza-Michael addition reaction between abranch polyamine and an activated olefin (α, β-unsaturated carbonylcompound) containing cationic group.

FIG. 3 shows the results of using several exemplary multiple chargedcationic compounds and one incumbent compound to treat a synthetic oilywater system.

FIG. 4 shows the results of using several exemplary multiple chargedcationic compounds and one incumbent compound to treat a waste watersystem from an oil refinery facility.

Various embodiments of the present disclosure will be described indetail with reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the disclosure. Figuresrepresented herein are not limitations to the various embodimentsaccording to the disclosure and are presented for exemplary illustrationof the disclosure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Disclosed herein are water clarification compositions comprising novelmultiple charged cationic or anionic compounds and methods of usingnovel multiple charged cationic or anion compounds in a waterclarification composition for clarifying a water system. Specifically,multiple charge cationic compounds having two or more positive chargesor anionic compounds having two or more negative compounds derived froma polyamine (Michael donor) and activated olefin (Michael acceptor)through an aza-Michael are used in a water clarification composition toclarify a water system.

The embodiments of this disclosure are not limited to particularcompositions and methods of use which can vary and are understood byskilled artisans. It is further to be understood that all terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting in any manner or scope. For example,as used in this specification and the appended claims, the singularforms “a,” “an” and “the” can include plural referents unless thecontent clearly indicates otherwise. Further, all units, prefixes, andsymbols may be denoted in its SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this disclosure are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the disclosure. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present disclosure may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe disclosure pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present disclosure without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present disclosure, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through error in these procedures; throughdifferences in the manufacture, source, or purity of the ingredientsused to make the compositions or carry out the methods; and the like.The term “about” also encompasses amounts that differ due to novelequilibrium conditions for a composition resulting from a particularinitial mixture. Whether or not modified by the term “about”, the claimsinclude equivalents to the quantities.

As used herein, “substituted” refers to an organic group as definedbelow (e.g., an alkyl group) in which one or more bonds to a hydrogenatom contained therein are replaced by a bond to non-hydrogen ornon-carbon atoms. Substituted groups also include groups in which one ormore bonds to carbon(s) or hydrogen(s) atom replaced by one or morebonds, including double or triple bonds, to a heteroatom. Thus, asubstituted group is substituted with one or more substituents, unlessotherwise specified. A substituted group can be substituted with 1, 2,3, 4, 5, or 6 substituents.

Substituted ring groups include rings and ring systems in which a bondto a hydrogen atom is replaced with a bond to a carbon atom. Therefore,substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups mayalso be substituted with substituted or unsubstituted alkyl, alkenyl,and alkynyl groups are defined herein.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and allcylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

Alkenyl groups or alkenes are straight chain, branched, or cyclic alkylgroups having two to about 30 carbon atoms, and further including atleast one double bond. In some embodiments, an alkenyl group has from 2to about 30 carbon atoms, or typically, from 2 to 10 carbon atoms.Alkenyl groups may be substituted or unsubstituted. For a double bond inan alkenyl group, the configuration for the double bond can be a transor cis configuration. Alkenyl groups may be substituted similarly toalkyl groups.

Alkynyl groups are straight chain, branched, or cyclic alkyl groupshaving two to about 30 carbon atoms, and further including at least onetriple bond. In some embodiments, an alkynyl group has from 2 to about30 carbon atoms, or typically, from 2 to about 10 carbon atoms. Alkynylgroups may be substituted or unsubstituted. Alkynyl groups may besubstituted similarly to alkyl or alkenyl groups.

As used herein, the terms “alkylene”, “cycloalkylene”, “alkynylides”,and “alkenylene”, alone or as part of another substituent, refer to adivalent radical derived from an alkyl, cycloalkyl, or alkenyl group,respectively, as exemplified by —CH₂CH₂CH₂—. For alkylene,cycloalkylene, alkynylene, and alkenylene groups, no orientation of thelinking group is implied.

The term“ester” as used herein refers to —R³⁰COOR³¹ group. R³⁰ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³¹ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “amine” (or “amino”) as used herein refers to —R³²NR³³R³⁴groups. R³² is absent, a substituted or unsubstituted alkylene,cycloalkylene, alkenylene, alkynylene, arylene, aralkylene,heterocyclylalkylene, or heterocyclylene group as defined herein. R³³and R³⁴ are independently hydrogen, or a substituted or unsubstitutedalkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl,or heterocyclyl group as defined herein.

The term “amine” as used herein also refers to an independent compound.When an amine is a compound, it can be represented by a formula ofR^(32′)NR^(33′)R^(34′) groups, wherein R^(32′), R^(33′), and R³⁴ areindependently hydrogen, or a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, orheterocyclyl group as defined herein.

The term “alcohol” as used herein refers to —R³⁵OH groups. R³⁵ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “carboxylic acid” as used herein refers to —R³⁶COOH groups. R³⁶is absent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “ether” as used herein refers to —R³⁷OR³⁸ groups. R³⁷ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³⁸ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “solvent” as used herein refers to any inorganic or organicsolvent. Solvents are useful in the disclosed method or article,product, or composition as reaction solvent or carrier solvent. Suitablesolvents include, but are not limited to, oxygenated solvents such aslower alkanols, lower alkyl ethers, glycols, aryl glycol ethers andlower alkyl glycol ethers. Examples of other solvents include, but arenot limited to, methanol, ethanol, propanol, isopropanol and butanol,isobutanol, ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, mixed ethylene-propylene glycolethers, ethylene glycol phenyl ether, and propylene glycol phenyl ether.Water is a solvent too. The solvent used herein can be of a singlesolvent or a mixture of many different solvents.

Glycol ethers include, but are not limited to, diethylene glycol n-butylether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, diethylene glycol t-butyl ether,dipropylene glycol n-butyl ether, dipropylene glycol methyl ether,dipropylene glycol ethyl ether, dipropylene glycol propyl ether,dipropylene glycol tert-butyl ether, ethylene glycol butyl ether,ethylene glycol propyl ether, ethylene glycol ethyl ether, ethyleneglycol methyl ether, ethylene glycol methyl ether acetate, propyleneglycol n-butyl ether, propylene glycol ethyl ether, propylene glycolmethyl ether, propylene glycol n-propyl ether, tripropylene glycolmethyl ether and tripropylene glycol n-butyl ether, ethylene glycolphenyl ether, propylene glycol phenyl ether, and the like, or mixturesthereof.

Acids

The compositions disclosed herein may include an acid. However, in someembodiments, the compositions disclosed herein are free of an acid.

Generally, acids, as used in this disclosure, include both organic andinorganic acids. Organic acids include, but not limited to,hydroxyacetic (glycolic) acid, formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid,trichloroacetic acid, urea hydrochloride, and benzoic acid. Organicacids also include dicarboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid,and terephthalic acid. Combinations of these organic acids can also beused. Inorganic acids include, but are not limited to, mineral acids,such as phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamicacid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitricacid. Inorganic acids can be used alone, in combination with otherinorganic acid(s), or in combination with one or more organic acid. Acidgenerators can be used to form a suitable acid, including for examplegenerators such as potassium fluoride, sodium fluoride, lithiumfluoride, ammonium fluoride, ammonium bifluoride, sodium silicofluoride,etc.

Examples of particularly suitable acids in this the methods orcompositions disclosed herein include inorganic and organic acids.Exemplary inorganic acids include phosphoric, phosphonic, sulfuric,sulfamic, methylsulfonic, hydrochloric, hydrobromic, hydrofluoric, andnitric. Exemplary organic acids include hydroxyacetic (glycolic),citric, lactic, formic, acetic, propionic, butyric, valeric, caproic,gluconic, itaconic, trichloroacetic, urea hydrochloride, and benzoic.Organic dicarboxylic acids can also be used such as oxalic, maleic,fumaric, adipic, and terephthalic acid.

Percarboxylic Acids and Peroxycarboxylic Acid Compositions

A peroxycarboxylic acid (i.e. peracid) or peroxycarboxylic acidcomposition can be included in the articles, products, or compositionsdisclosed herein. As used herein, the term “peracid” may also bereferred to as a “percarboxylic acid,” “peroxycarboxylic acid” or“peroxyacid.” Sulfoperoxycarboxylic acids, sulfonated peracids andsulfonated peroxycarboxylic acids are also included within the terms“peroxycarboxylic acid” and “peracid” as used herein. As one of skill inthe art appreciates, a peracid refers to an acid having the hydrogen ofthe hydroxyl group in carboxylic acid replaced by a hydroxy group.Oxidizing peracids may also be referred to herein as peroxycarboxylicacids.

A peracid includes any compound of the formula R—(COOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroalkyl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein.

A peroxycarboxylic acid composition, as used herein, refers to anycomposition that comprises one or more peracids, their correspondingacids, and hydrogen peroxide or or other oxidizing agents. Aperoxycarboxylic acid composition can also include a stabilizer,fluorescent active tracer or compound, or other ingredients, as oneskilled in the other would know.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid. Peracids such as peroxyacetic acid andperoxyoctanoic acid may also be used. Any combination of these acids mayalso be used.

In some embodiments, however, the articles, products, or compositionsdisclosed herein are free of a peroxycarboxylic acid or peroxycarboxylicacid composition.

Alkalinity Source or Base

The compositions disclosed herein may include an alkalinity source or abase. However, in some embodiments, the compositions disclosed hereinare free of a base or alkalinity source.

The alkalinity source in turn comprises one or more bases or alkalinecompounds. In general, an effective amount of the alkalinity sourceshould be considered as an amount that provides the composition or usesolution of the composition having a pH of at least about 8. When theuse solution has a pH of between about 8 and about 10, it can beconsidered mildly alkaline, and when the pH is greater than about 12,the solution can be considered caustic.

The alkalinity source can include an alkali metal carbonate, an alkalimetal hydroxide, alkaline metal silicate, alkaline metal metasilicate,or a mixture thereof. Suitable metal carbonates that can be usedinclude, for example, sodium or potassium carbonate, bicarbonate,sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxidesthat can be used include, for example, sodium, lithium, or potassiumhydroxide. Examples of useful alkaline metal silicates include sodium orpotassium silicate (with M₂O:SiO₂ ratio of 2.4 to 5:1, M representing analkali metal) or metasilicate. A metasilicate can be made by mixing ahydroxide and silicate. The alkalinity source may also include a metalborate such as sodium or potassium borate, and the like.

The alkalinity source may also include ethanolamines, urea sulfate,amines, amine salts, and quaternary ammonium. The simplest cationicamines, amine salts and quaternary ammonium compounds can beschematically drawn thus:

in which, R represents a long alkyl chain, R′, R″, and R′″ may be eitherlong alkyl chains or smaller alkyl or aryl groups or hydrogen and Xrepresents an anion.

In some embodiments, the compositions are free of the alkalinity sourceor base.

Polyamines

A polyamine can have, but is limited to, a generic formula ofNH₂—[R^(10′)]_(n)—NH₂, (RNH)_(n)—RNH₂, H₂N—(RNH)_(n)—RNH₂, orH₂N—(RN(R′))_(n)—RNH₂, wherein R^(10′) is a linear or branched,unsubstituted or substituted C₂-C₁₀ alkylene group, or combinationthereof; R is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear orbranched, unsubstituted or substituted C₄-C₁₀ alkylene group, orcombination thereof; R′ is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, alinear or branched, unsubstituted or substituted C₄-C₁₀ alkyl group,RNH₂, RNHRNH₂, or RN(RNH₂)₂; and n can be from 2 to 1,000,000. Themonomer in a polyamine, e.g., the R or R′ group, can be the same ordifferent. In this disclosure, a polyamine refers to both small moleculepolyamine when n is from 1 to 9 and polymeric polyamine when n is from10 to 1,000,000.

Small molecule polyamines include, but are not limited toethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine,and tris(2-aminoethyl)amine.

Other possible polyamines include JEFFAMINE® monoamines, diamines, andtriamines by Huntsman. These highly versatile products contain primaryamino groups attached to the end of a polyether backbone normally basedon propylene oxide (PO), ethylene oxide (EO), or a mixture of bothoxides. JEFFAMINE® amines include a polyetheramine family consisted ofmonoamines, diamines and triamines based on the core polyether backbonestructure. JEFFAMINE® amines also include high-conversion, andpolytetramethylene glycol (PTMEG) based polyetheramines. TheseJEFFAMINE® amines have an average molecular weight (M_(w)) of from about130 to about 4,000.

A polyamine used in this disclosure can be a polyamine derivative ormodified polyamine, in which one or more of the NH protons, but not all,in the polyamine is substituted by an unsubstituted or substitutedgroup. For example, an alkyl polyamine that contains one or more alkylgroup connected to the nitrogen atom can be used to produce the multiplecharged cationic or anionic compounds disclosed herein. In these PEIderivatives, only some of primary NH₂ or secondary NH protons arereplaced by other non-proton groups and the remaining NH₂ or NH protonscan still react with a Michael acceptor, such as an activated olefincontaining a hydrophilic (ionic) group, by an aza-Michael Additionreaction.

One class of the polymeric polyamine includes polyethyleneimine (PEI)and its derivatives. Polyethyleneimine (PEI) or polyaziridine is apolymer with a repeating unit of CH₂CH₂NH and has a general formulationof NH₂(CH₂CH₂NH)_(n)—CH₂CH₂NH₂, wherein n can be from 2 to 10⁵. Therepeating monomer in PEI has a molecular weight of 43.07 and a nitrogento carbon ratio of 1:2.

PEIs and their derivatives can linear, branched, or dendric. Linearpolyethyleneimines contain all secondary amines, in contrast to branchedPEIs which contain primary, secondary and tertiary amino groups. Totallybranched, dendrimeric forms also exist and contain primary and tertiaryamino groups. Drawings for unmodified linear, branched, and dendrimericPEI are shown below.

PEI derivatives are usually obtained by substituting proton(s) on thenitrogen atoms with different group. One such PEI derivative isethoxylated and propoxylated PEI, wherein the polyethyleneimines arederivatized with ethylene oxide (EO) and/or propylene oxide (PO) sidechains. Ethoxylation of PEIs can increase the solubility of PEIs.

PEI is produced on industrial scale. Various commercialpolyethyleneimines are available, including for example those sold underthe tradename Lupasol® (BASF), including for example Lupasol® FG,Lupasol® G, Lupasol® PR 8515, Lupasol® WF, Lupasol® G 20/35/100,Lupasol® HF, Lupasol® P, Lupasol® PS, Lupasol® PO 100, Lupasol® PN50/60, and Lupasol® SK. These PEIs have average molecular weights(M_(w)) of about 800, about 1,300, about 2,000, about 5,000, about25,000, about 1,300/2,000/5,000, about 25,000, about 750,000, about750,000, about 1,000,000, and about 2,000,000, respectively.

Two common used averages for molecular weight of a polymer are numberaverage molecular weight (M_(n)) and weight average molecular weight(M_(w)). The polydispersity index (D) represents the molecular weightdistribution of the polymers. Mn=(ρn_(i)M_(i))/Σn_(i),M_(w)=(Σn_(i)M_(i) ²)/Σn_(i)M_(i), and D=M_(w)/M_(n), wherein the indexnumber, i, represents the number of different molecular weights presentin the sample and n_(i) is the total number of moles with the molar massof M_(i). For a polymer, M_(n) and M_(w) are usually different. Forexample, a PEI compound can have a M_(n) of about 10,000 by GPC andM_(w) of about 25,000 by LS.

Light Scattering (LS) can be used to measure M_(w) of a polymer sample.Another easy way to measure molecular weight of a sample or product isgel permeation chromatography (GPC). GPC is an analytical technique thatseparates molecules in polymers by size and provides the molecularweight distribution of a material. GPC is also sometimes known as sizeexclusion chromatography (SEC). This technique is often used for theanalysis of polymers for their both M_(n) and M_(w).

These commercially available and exemplary polyethyleneimines aresoluble in water and available as anhydrous polyethyleneimines and/ormodified polyethyleneimines provided in aqueous solutions ormethoxypropanol (as for Lupasol® PO 100).

Suitable polyethyleneimine useful in the present disclosure may containa mixture of primary, secondary, and tertiary amine substituents ormixture of different average molecular weights. The mixture of primary,secondary, and tertiary amine substituents may be in any ratio,including for example in the ratio of about 1:1:1 to about 1:2:1 withbranching every 3 to 3.5 nitrogen atoms along a chain segment.Alternatively, suitable polyethyleneimine compounds may be primarily oneof primary, secondary or tertiary amine substituents.

The polyamine that can be used to make the multiple charged cationic oranionic compounds disclosed herein can have a wide range of its averagemolecular weight. Different multiple charged cationic or anioniccompounds with their characteristic average molecular weights can beproduced by selecting different starting small molecule polyamines,polymeric PEIs, or mixture thereof. Controlling the size of polyaminesor PEI and extent of modification by the activated olefin containingionic groups, one can produce the multiple charged cationic or anioniccompounds with a similar average molecular weight and multiple cationiccharges or multiple anionic charges. Because of this character, one canproduce and use different multiple charged cationic or anionic compoundsfor a wider range of applications that are using unmodified polyamine orPEIs.

Specifically, the polyamines that can be used to make the multiplecharged cationic or anionic compounds disclosed here have an averagemolecular weight (M_(w)) of about 60-200, about 100-400, about 100-600,about 600-5,000, about 600-800, about 800-2,000, about 800-5,000, about100-2,000,000, about 100-25,000, about 600-25,000, about 800-25,000,about 600-750,000, about 800-750,000, about 25,000-750,000, about750,000-2,000,000, about 100, about 200, about 300, about 400, about500, about 600, about 700, about 800, about 1,000, about 1,500, about2,000, about 3,000, about 5,000, about 8,000, about 10,000, about15,000, about 20,000, about 50,000, about 100,000, about 250,000, about500,000, about 1,000;000, 2,000,000, or any value there between.

Aza-Michael Addition Reaction Between a Polyamine and Activated Olefin

The multiple charged cationic or anionic compounds in the reverseemulsion breaker compositions disclosed herein are derived from anaza-Michael Addition Reaction between a polyamine and an activatedolefin containing a hydrophilic ionic group.

An aliphatic amine group may undergo an aza-Michael Addition reactionwhen in contact with an unsaturated hydrocarbon moiety (e.g.,carbon-carbon double bond) that is in proximity of an electronwithdrawing group such as carbonyl, cyano, or nitro group. Specifically,the Michael addition is a reaction between nucleophiles and activatedolefin and alkyne functionalities, wherein the nucleophile adds across acarbon-carbon multiple bond that is adjacent to an electron withdrawingand resonance stabilizing activating group, such as a carbonyl group.The Michael addition nucleophile is known as the “Michael donor”, theactivated electrophilic olefin is known as the “Michael acceptor”, andreaction product of the two components is known as the “Michael adduct.”Examples of Michael donors include, but are not restricted to, amines,thiols, phosphines, carbanions, and alkoxides. Examples of Michaelacceptors include, but are not restricted to, acrylate esters, alkylmethacrylates, acrylonitrile, acrylamides, maleimides, cyanoacrylatesand vinyl sulfones, vinyl ketones, nitro ethylenes, α,β-unsaturatedaldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, azocompounds, beta-keto acetylenes and acetylene esters.

As used herein, an “activated olefin” refers to a substituted alkene inwhich at least one of the double-bond carbon has a conjugated electronwithdrawing group. Examples of activated olefins include, but notlimited to, α, β-unsaturated carbonyl compounds (such asCH₂═CHCO—NH—CH₃, alkyl-CH═CH—CO-alkyl, CH₂═CH₂C(O)—O—CH₃), CH₂═CH—COOH,CH₂═CH(CH₃)—COOH, CH₂═CH—SO₃H, and like.

It was found that the Aza-Michael addition can be used to synthesize thedisclosed compounds without having to use a higher temperature greaterthan 200° C. and high pressure greater than normal atmosphere pressureand with a high yield (greater than 98%), sometimes within about 24hours.

Aza-Michael addition reaction can be catalyzed by a strong acid or base.In some cases, some ionic liquids can function both as reaction mediaand catalyst. The preferred catalyst for the Aza-Michael additionreaction to synthesize the disclosed compounds is a base. Exemplary basecatalyst can be hydroxide and amines. Because the reaction to synthesizethe disclosed compounds uses a polyamine that usually include a primaryamine group, the primary amine group itself can function as a catalystfor the reaction. In such embodiments, no additional catalyst isnecessary, or an additional catalyst is optional. Other preferredcatalysts include amidine and guanidine bases.

The use of solvent and/or diluent for the reaction is optional. Whenemployed, a wide range of non-acidic solvents are suitable, such as, forexample, water, ethers (e.g., tetrahydrofuran (THF)), aromatichydrocarbons (e.g., toluene and xylene), alcohols (e.g., n-butanol),esters (e.g., ethyl 3-ethoxypropionate), and the like. A wide range ofsolvents can be used for the reaction because the synthesis process isrelatively insensitive to solvent. When solvent (or diluent) isemployed, loading levels can range from as low as about 10 wt-% up toabout 80 wt-% and higher. The solvent loading level can be about 0 wt-%,from about 1 wt-% to about 10 wt-%, from about 10 wt-% to about 20 wt-%,from about 20 wt-% to about 30 wt-%, from about 30 wt-% to about 40wt-%, from about 40 wt-% to about 50 wt-%, from about 50 wt-% to about60 wt-%, from about 60 wt-% to about 70 wt-%, from about 70 wt-% toabout 80 wt-%, from about 1 wt-% to about 20 wt-%, from about 20 wt-% toabout 40 wt-%, from about 40 wt-% to about 60 wt-%, from about 60 wt-%to about 80 wt-%, from about 40 wt-% to about 70 wt-%, at least about 5wt-%, about 15 wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about55 wt-%, about 65 wt-%, about 75 wt-%, or any value there between of thefinal reaction mixture.

Generally, the reaction can be carried out at a temperature over a widerange of temperatures. The reaction temperature can range from about 0°C. to about 150° C., more preferably from about 50° C. to about 80° C.The temperature for contacting the polyamine and activated olefin can befrom about 10° C. to about 140° C., about 20° C. to about 130° C., about30° C. to about 120° C., about 40° C. to about 110° C., about 50° C. toabout 100° C., about 60° C. to about 90° C., about 70° C. to about 80°C., about 0° C. to about 20° C., about 20° C. to about 40° C., about 40°C. to about 60° C., about 60° C. to about 80° C., about 80° C. to about100° C., about 100° C. to about 120° C., about 120° C. to about 150° C.,about 5° C., about 25° C., about 45° C., about 65° C., about 85° C.,about 105° C., about 125° C., about 145° C., or any value there between.The reaction temperature can be about the same from starting of thereaction to end of the reaction or can be changed from one temperatureto another while the reaction is going on.

The reaction time for the synthesis of the compounds disclosed hereincan vary widely, depending on such factors as the reaction temperature,the efficacy and amount of the catalyst, the presence or absence ofdiluent (solvent), and the like. The preferred reaction time can be fromabout 0.5 hours to about 48 hours, from about 1 hour to about 40 hours,from about 2 hours to about 38 hours, from about 4 hours to about 36hours, from 6 hours to about 34 hours, from about 8 hours to about 32hours, from about 10 hours to about 30 hours, from about 12 hours toabout 28 hours, from about 14 hours to 26 hours, from about 16 hours to24 hours, from about 18 hours to 20 hours, from about 1 hour to 8 hours,from 8 hours to 16 hours, from 8 hours to about 24 hours, about 2 hours,about 4 hours, about 6 hours, about 8 hours, about 10 hours, about 14hours, about 16 hours, about 18 hours, about 24 hours, about 30 hours,about 36 hours, or any values there between.

The reaction for the synthesis of the compounds disclosed herein can goto completion when one mole of the polyamine and two or more moles ofthe activated olefin are mixed together for a sufficient of time at atemperature described above.

The progression of the reaction can be typically monitored by ESI-MSand/or NMR spectroscopy for consumption of the monomer. The reactionproducts can be purified or separated by HPLC or other methods known byone skilled in the art. For reactions that proceeded to completion, theformed product can be separated by removal of solvent or byprecipitation in a non-polar solvent that was the opposite of thereaction media. For the reactions in water, the formed product isprecipitated from the aqueous reaction mixture. Higher pressure canspeed-up the reaction. In some embodiments, if the reaction is carriedout at a room temperature, the reaction can have a product yield of morethan 98%, in some embodiments within about 16 hours.

Other Water Clarification Composition Agent in a Water ClarificationComposition

In addition to the multiple charged cationic or anionic compoundsderived from polyamine as described herein, a water clarificationcomposition in the present disclosure includes one or more additionalwater clarification composition agents.

The additional water clarification composition agent in the disclosedwater clarification compositions can include, but is not limited to, anacid, carrier, dispersant, biocide, corrosion inhibitor, antioxidant,polymer degradation prevention agent, permeability modifier, foamingagent, antifoaming agent, fracturing proppant, glass particulate, sand,fracture proppant/sand control agent, scavenger for H₂S, CO₂, and/or O₂,gelling agent, lubricant, and friction reducing agent, salt, or mixturethereof.

The additional water clarification composition agent in the disclosedwater clarification compositions can also include, but not be limitedto, an organic sulfur compound, de-emulsifier, asphaltene inhibitor,paraffin inhibitor, scale inhibitor, water clarifier, emulsion breaker,reverse emulsion breaker, gas hydrate inhibitor, a pH modifier, asurfactant, or a combination thereof.

Furthermore, the additional water clarification composition agent can bea sequestrant, solubilizer, lubricant, buffer, cleaning agent, rinseaid, preservative, binder, thickener or other viscosity modifier,processing aid, carrier, water-conditioning agent, or foam generator,threshold agent or system, aesthetic enhancing agent (e.g., dye,odorant, perfume), or other additive suitable for formulation with areverse emulsion breaker, or mixtures thereof.

The additional water clarification composition agent in a waterclarification composition will vary according to the particular waterclarification composition being manufactured and its intend use as oneskilled in the art will appreciate.

Alternatively, the water clarification composition does not contain oris free of one or more of the additional water clarification compositionagents.

When one or more additional water clarification composition agents areused for preventing microbial or biofilm growth, they can be formulatedtogether with the multiple charged cationic compounds derived from aprimary or polyamine as described herein the same water clarificationcomposition. Alternatively, some or all the additional waterclarification composition agents can be formulated into one or moredifferent formulations and be supplied to the water system. In otherwords, the additional water clarification composition agents can beprovided into a water system independently, simultaneously, orsequentially.

Biocide and Carrier

In some embodiments, the water clarification compositions disclosedherein further include a biocide. In some other embodiments, thedisclosed water clarification compositions herein further include acarrier. In some other embodiments, the disclosed water clarificationcompositions herein further include a biocide and carrier. In someembodiments, the disclosed methods or water clarification compositionsherein may consist of one or more multiple charged cationic or anioniccompounds disclosed herein and carrier. In some embodiments, the waterclarification compositions disclosed herein consist of one or moremultiple charged cationic or cationic compounds disclosed herein, acarrier, and a biocide.

Biocides suitable for use may be oxidizing or non-oxidizing biocides.Oxidizing biocides include, but are not limited to, bleach, chlorine,bromine, chlorine dioxide, peroxycarboxylic acid, peroxycarboxylic acidcomposition, and materials capable of releasing chlorine, bromine, or aperoxide. Non-oxidizing biocides include, but are not limited to,glutaraldehyde, isothiazolin, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3 diol,1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile,tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride,dimethyl dialkyl ammonium chloride, didecyl dimethyl ammonium chloride,poly(oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride, methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol,2-(2-bromo-2-nitroethenyl)furan, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furan, 2-bromo-2-bromomethylglutaronitrile, bis(trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethanesulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-bromo-4′-hydroxyacetophenone,1,4-bis(bromoacetoxy)-2-butene, bis(tributyltin)oxide,2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-hiazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coco alkyldimethylamine oxide,n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride,7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid,4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one.

Suitable non-oxidizing biocides also include, for example, aldehydes(e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds(e.g., quaternary amine compounds and cocodiamine), halogenatedcompounds (e.g., 2-bromo-2-nitropropane-3-diol (Bronopol) and2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g.,isothiazolone, carbamates, and metronidazole), and quaternaryphosphonium salts (e.g., tetrakis(hydroxymethyl)-phosphonium sulfate(THPS)).

Suitable oxidizing biocides include, for example, sodium hypochlorite,trichloroisocyanuric acids, dichloroisocyantuic acid, calciumhypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilizedsodium hypobromite, activated sodium bromide, brominated hydantoins,chlorine dioxide, ozone, peroxycarboxylic acid, peroxycarboxylic acidcomposition, and peroxides.

The composition can comprise from about 0.1 wt-% to about 10 wt-%, fromabout 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-%of a biocide, based on total weight of the composition.

A carrier in the disclosed water clarification composition can be water,an organic solvent, or a combination of water and an organic solvent.The organic solvent can be an alcohol, a hydrocarbon, a ketone, anether, an alkylene glycol, a glycol ether, an amide, a nitrile, asulfoxide, an ester, or a combination thereof. Examples of suitableorganic solvents include, but are not limited to, methanol, ethanol,propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol,decanol, 2-butoxyethanol, methylene glycol, ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, diethyleneglycol monomethylether, diethylene glycol monoethyl ether, ethylene glycol monobutylether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane,methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene,heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether,propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, or acombination thereof.

The composition can comprise from about 1 wt-% to about 80 wt-%, fromabout 5 wt-% to about 50 wt-%, from about 5 wt-% to about 45 wt-%, fromabout 5 wt-% to about 30 wt-%, from about 5 wt-% to about 25 wt-%, fromabout 5 wt-% to about 20 wt-%, from about 5 wt-% to about 15 wt-%, fromabout 5 wt-% to about 10 wt-%, from about 10 wt-% to about 35 wt-%, fromabout 10 wt-% to about 25 wt-%, or from about 10 wt-% to about 35 wt-%of the one or more carriers, based on total weight of the composition.

Corrosion Inhibitor

In some embodiments, the water clarification compositions disclosedherein further include a corrosion inhibitor. In some other embodiments,the disclosed water clarification compositions herein further include acorrosion inhibitor and carrier. In some other embodiments, thedisclosed water clarification compositions herein further include acorrosion inhibitor, biocide, and carrier. In some embodiments, thedisclosed water clarification compositions herein may consist of one ormore multiple charged cationic or anionic compounds disclosed herein,one or more corrosion inhibitors and carrier. In some embodiments, thewater clarification compositions disclosed herein consist of one or moremultiple charged cationic or anionic compounds disclosed herein, acarrier, corrosion inhibitor, and a biocide. In some embodiments, thebiocide is an oxidizing biocide. In some other embodiments, the biocideis a non-oxidizing biocide.

The water clarification composition can comprise from about 0.1 wt-% toabout 20 wt-%, from about 0.1 wt-% to about 10 wt-%, or from 0.1 toabout 5 wt-% of one or more , corrosion inhibitors, based on totalweight of the composition. A composition disclosed herein can comprisefrom 0 wt-% to about 10 wt-% of the one or more corrosion inhibitors,based on total weight of the composition. The composition can compriseabout 1.0 wt-%, about 1.5 wt-%, about 2.0 wt-%, about 2.5 wt-%, about3.0 wt-%, about 3.5 wt-%, about 4.0 wt-%, about 4.5 wt-%, about 5.0wt-%, about 5.5 wt-%, about 6.0 wt-%, about 6.5 wt-%, about 7.0 wt-%,about 7.5 wt-%, about 8.0 wt-%, about 8.5 wt-%, about 9.0 wt-%, about9.5 wt-%, about 10.0 wt-%, about 10.5 wt-%, about 11.0 wt-%, about 11.5wt-%, about 12.0 wt-%, about 12.5 wt-%, about 13.0 wt-%, about 13.5wt-%, about 14.0 wt-%, about 14.5 wt-%, or about 15.0 wt-% of the one ormore corrosion inhibitors, based on total weight of the composition.Each water system can have its own requirements for using a corrosioninhibitor, and the weight percent of one or more corrosion inhibitors inthe composition can vary with the water system in which it is used.

A corrosion inhibitor is needed to reduce corrosion of metals in thewater system. Corrosion inhibitors for multi-metal protection aretypically triazoles, such as, but not limited to, benzotriazole,halogenated triazoles, and nitro-substituted azoles.

The one or more corrosion inhibitors can be an imidazoline compound, aquatemary ammonium compound, a pyridinium compound, or a combinationthereof.

The one or more corrosion inhibitor component can be an imidazoline. Theimidazoline can be, for example, imidazoline derived from a diamine,such as ethylene diamine (EDA), diethylene triamine (DETA), triethylenetetraamine (TETA) etc. and a long chain fatty acid such as tall oilfatty acid (TOFA). The imidazoline can be an imidazoline of Formula (1A)or an imidazoline derivative. Representative imidazoline derivativesinclude an imidazolinium compound of Formula (2A) or a bis-quatemizedcompound of Formula (3A).

The one or more corrosion inhibitor component can include an imidazolineof Formula (1A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)is hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆ arylalkyl; andR^(12a) and R^(13a) are independently hydrogen or a C₁-C₆ alkyl group.Preferably, the imidazoline includes an R^(10a) which is the alkylmixture typical in tall oil fatty acid (TOFA), and R^(11a), R^(12a) andR^(13a) are each hydrogen.

The one or more additional corrosion inhibitor component can be animidazolinium compound of Formula (2A):

wherein R^(10a) is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R^(11a)and R^(14a) are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,or C₁-C₆ arylalkyl; R^(12a) and R^(13a) are independently hydrogen or aC₁-C₆ alkyl group; and X⁻ is a halide (such as chloride, bromide, oriodide), carbonate, sulfonate, phosphate, or the anion of an organiccarboxylic acid (such as acetate). Preferably, the imidazoliniumcompound includes 1-benzyl-1-(2-hydroxyethyl)-2-tall-oil-2-imidazoliniumchloride.

The one or more additional corrosion inhibitors can be a bis-quatemizedcompound having the formula (3A):

wherein R^(1a) and R^(2a) are each independently unsubstituted branched,chain or ring alkyl or alkenyl having from 1 to about 29 carbon atoms;partially or fully oxygenized, sulfurized, and/or phosphorylizedbranched, chain, or ring alkyl or alkenyl having from 1 to about 29carbon atoms; or a combination thereof; R^(3a) and R^(4a) are eachindependently unsubstituted branched, chain or ring alkylene oralkenylene having from 1 to about 29 carbon atoms; partially or fillyoxygenized, sulfurized, and/or phosphorylized branched, chain, or ringalkylene or alkenylene having from 1 to about 29 carbon atoms; or acombination thereof; L₁ and L₂ are each independently absent, H, —COOH,—SO₃H, —PO₃H, —COOR^(5a), —CONH₂, —CONHR^(5a), or —CON(R^(5a))₂; R^(5a)is each independently a branched or unbranched alkyl, aryl, alkylaryl,alkylheteroaryl, cycloalkyl, or heteroaryl group having from 1 to about10 carbon atoms; n is 0 or 1, and when n is 0, L2 is absent or H; x isfrom 1 to about 10; and y is from 1 to about 5. Preferably, R^(1a) andR^(2a) are each independently C₆-C₂₂ alkyl, C₈-C₂₀ alkyl, C₁₂-C₁₈ alkyl,C₁₆-C₁₈ alkyl, or a combination thereof; R^(3a) and R^(4a) are C₁-C₁₀alkylene, C₂-C₈ alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; n is 0 or1; x is 2; y is 1; R₃ and R₄ are —C₂H₂—; L₁ is —COOH, —SO₃H, or —PO₃H;and L₂ is absent, H, —COOH, —SO₃H, or —PO₃H. For example, R^(1a) andR^(2a) can be derived from a mixture of tall oil fatty acids and arepredominantly a mixture of C₁₇H₃₃ and C₁₇H₃₁ or can be C₁₆-C₁₈ alkyl;R^(3a) and R^(4a) can be C₂-C₃ alkylene such as —C₂H₂—; n is 1 and L₂ is—COOH or n is 0 and L₂ is absent or H; x is 2; y is 1; R^(3a) and R^(4a)are —C₂H₂—; and L₁ is —COOH.

It should be appreciated that the number of carbon atoms specified foreach group of formula (3A) refers to the main chain of carbon atoms anddoes not include carbon atoms that may be contributed by substituents.

The one or more corrosion inhibitors can be a bis-quaternizedimidazoline compound having the formula (3A) wherein R^(1a) and R^(3a)are each independently C₆-C₂₂ alkyl, C₈-C₂₀ alkyl, C₁₂-C₁₈ alkyl, orC₁₆-C₁₈ alkyl or a combination thereof; R^(4a) is C₁-C₁₀ alkylene, C₂-C₈alkylene, C₂-C₆ alkylene, or C₂-C₃ alkylene; x is 2; y is 1; n is 0; L₁is —COOH, —SO₃H, or —PO₃H; and L₂ is absent or H. Preferably, abis-quaterized compound has the formula (3A) wherein R^(1a) and R^(2a)are each independently C₁₆-C₁₈ alkyl; R^(4a) is —C₂H₂—; x is 2; y is 1;n is 0; L₁ is —COOH, —SO₃H, or —PO₃H and L₂ is absent or H.

The one or more corrosion inhibitors can be a quaternary ammoniumcompound of Formula (4A):

wherein R^(1a), R^(2a), and R^(3a) are independently C₁ to C₂₀ alkyl,R^(4a) is methyl or benzyl, and X⁻ is a halide or methosulfate.

Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl or aryl aminequaternary salts include those alkylaryl, arylalkyl and aryl aminequaternary salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] whereinR^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbon atoms, and Xis Cl, Br or I. For the quaternary salts, R^(5a), R^(6a), R^(7a), andR^(8a) can each be independently alkyl (e.g., C₁-C₁₈ alkyl),hydroxyalkyl (e.g., C₁-C₁₈ hydroxyalkyl), and arylalkyl (e.g., benzyl).The mono or polycyclic aromatic amine salt with an alkyl or alkylarylhalide include salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻]wherein R^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbonatoms and at least one aryl group, and X is Cl, Br, or I.

Suitable quaternary ammonium salts include, but are not limited to, atetramethyl ammonium salt, a tetraethyl ammonium salt, a tetrapropylammonium salt, a tetrabutyl ammonium salt, a tetrahexyl ammonium salt, atetraoctyl ammonium salt, a benzyltrimethyl ammonium salt, abenzyltriethyl ammonium salt, a phenyltrimethyl ammonium salt, aphenyltriethyl ammonium salt, a cetyl benzyldimethyl ammonium salt, ahexadecyl trimethyl ammonium salt, a dimethyl alkyl benzyl quaternaryammonium salt, a monomethyl dialkyl benzyl quaternary ammonium salt, ora trialkyl benzyl quaternary ammonium salt, wherein the alkyl group hasabout 6 to about 24 carbon atoms, about 10 and about 18 carbon atoms, orabout 12 to about 16 carbon atoms. The quaternary ammonium salt can be abenzyl trialkyl quaternary ammonium salt, a benzyl triethanolaminequaternary ammonium salt, or a benzyl dimethylaminoethanolaminequaternary ammonium salt.

The one or more corrosion inhibitor component can be a pyridinium saltsuch as those represented by Formula (5A):

wherein R^(9a) is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms and X⁻ isa halide such as chloride, bromide, or iodide. Among these compounds arealkyl pyridinium salts and alkyl pyridinium benzyl quats. Exemplarycompounds include methyl pyridinium chloride, ethyl pyridinium chloride,propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridiniumchloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetylpyridinium chloride, benzyl pyridinium chloride and an alkyl benzylpyridinium chloride, preferably wherein the alkyl is a C₁-C₆ hydrocarbylgroup. Preferably, the pyridinium compound includes benzyl pyridiniumchloride.

The one or more additional corrosion inhibitors can be a phosphateester, monomeric or oligomeric fatty acid, alkoxylated amine, or mixturethereof.

The one or more corrosion inhibitor component can be a phosphate ester.Suitable mono-, di- and tri-alkyl as well as alkylaryl phosphate estersand phosphate esters of mono, di, and triethanolamine typically containbetween from 1 to about 18 carbon atoms. Preferred mono-, di-andtrialkyl phosphate esters, alkylaryl or arylalkyl phosphate esters arethose prepared by reacting a C₃-C₁₈ aliphatic alcohol with phosphorouspentoxide. The phosphate intermediate interchanges its ester groups withtriethylphosphate producing a broader distribution of alkyl phosphateesters.

Alternatively, the phosphate ester can be made by admixing with an alkyldiester, a mixture of low molecular weight alkyl alcohols or diols. Thelow molecular weight alkyl alcohols or diols preferably include C₆ toC₁₀ alcohols or diols. Further, phosphate esters of polyols and theirsalts containing one or more 2-hydroxyethyl groups, and hydroxylaminephosphate esters obtained by reacting polyphosphoric acid or phosphoruspentoxide with hydroxylamines such as diethanolamine or triethanolamineare preferred.

The one or more corrosion inhibitors can be a monomeric or oligomericfatty acid. Preferred monomeric or oligomeric fatty acids are C₁₄-C₂₂saturated and unsaturated fatty acids as well as dimer, trimer andoligomer products obtained by polymerizing one or more of such fattyacids.

The one or more corrosion inhibitors can be an alkoxylated amine. Thealkoxylated amine can be an ethoxylated alkyl amine. The alkoxylatedamine can be ethoxylated tallow amine.

Dispersant

In some embodiments, the water clarification compositions disclosedherein can further comprise a dispersant. A dispersant keeps particulatematter present in the water of a water system dispersed, so that it doesnot agglomerate. The composition can comprise can comprise from about0.1 wt-% to about 10 wt-%, from about 0.5 wt-% to about 5 wt-%, or fromabout 0.5 wt-% to about 4 wt-% of a dispersant, based on total weight ofthe composition.

A dispersant may be an acrylic acid polymer, maleic acid polymer,copolymer of acrylic acid with sulfonated monomers, alkyl estersthereof, or combination thereof. These polymers may include terpolymersof acrylic acid, acrylamide and sulfonated monomers. These polymers mayalso include quad-polymers consisting of acrylic acid and three othermonomers.

Suitable dispersants include, but are not limited to, aliphaticphosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonicacid, and aminoalkyl phosphonic acids, e.g. polyaminomethylenephosphonates with 2-10 N atoms e.g. each bearing at least one methylenephosphonic acid group; examples of the latter are ethylenediaminetetra(methylene phosphonate), diethylenetriamine penta(methylenephosphonate), and the triamine- and tetramine-polymethylene phosphonateswith 2-4 methylene groups between each N atom, at least 2 of the numbersof methylene groups in each phosphonate being different. Other suitabledispersion agents include lignin, or derivatives of lignin such aslignosulfonate and naphthalene sulfonic acid and derivatives.

Other Additional Water Clarification Composition Agents

In some embodiments, the water clarification compositions disclosedherein further include an additional water clarification compositionagent. The additional water clarification composition agent can be anorganic sulfur compound, de-emulsifier, an asphaltene inhibitor, aparaffin inhibitor, a scale inhibitor, an emulsifier, a water clarifier,an emulsion breaker, a gas hydrate inhibitor, a pH modifier, asurfactant, or a combination thereof.

The water clarification composition can further comprise an organicsulfur compound, such as a mercaptoalkyl alcohol, mercaptoacetic acid,thioglycolic acid, 3,3′-dithiodipropionic acid, sodium thiosulfate,thiourea, L-cysteine, tert-butyl mercaptan, sodium thiosulfate, ammoniumthiosulfate, sodium thiocyanate, ammonium thiocyanate, sodiummetabisulfite, or a combination thereof. Preferably, the mercaptoallcylalcohol comprises 2-mercaptoethanol. Such compounds are used assynergists in the composition. The organic sulfur compound canconstitute from about 0.5 wt-% to about 15 wt-% of the composition,based on total weight of the composition, preferably about 1 wt-% toabout 10 wt-% and more preferably from about 1 wt-% to about 5 wt-%. Theorganic sulfur compound can about 1 wt-%, about 2 wt-%, about 3 wt-%,about 4 wt-%, about 5 wt-%, about 6 wt-%, about 7 wt-%, about 8 wt-%,about 9 wt-%, about 10 wt-%, about 11 wt-%, about 12 wt-%, about 13wt-%, about 14 wt-%, or about 15 wt-% of the composition.

The water clarification composition can further comprise ade-emulsifier. Preferably, the demulsifier comprises an oxyalkylatepolymer, such as a polyalkylene glycol. The de-emulsifier can constitutefrom about 0.1 wt-% to about 10 wt-%, from about 0.5 wt-% to about 5 wt.%, or from about 0.5 wt-% to about 4 wt-% of the composition, based ontotal weight of the composition. The de-emulsifier can constitute about0.5 wt-%, about 1 wt-%, about 1.5 wt-%, about 2 wt-%, about 2.5 wt-%,about 3 wt-%, about 3.5 wt-%, about 4 wt-%, about 4.5 wt-%, or about 5wt-% of the composition.

The water clarification composition can further comprise an asphalteneinhibitor. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.1 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of an asphaltene inhibitor, based on total weight of thecomposition. Suitable asphaltene inhibitors include, but are not limitedto, aliphatic sulfonic acids; alkyl aryl sulfonic acids; arylsulfonates; lignosulfonates; alkylphenol/aldehyde resins and similarsulfonated resins; polyolefin esters; polyolefm imides; polyolefinesters with alkyl, alkylenephenyl or alkylenepyridyl functional groups;polyolefin amides; polyolefin amides with alkyl, alkylenephenyl oralkylenepyridyl functional groups; polyolefm imides with alkyl,alkylenephenyl or alkylenepyridyl functional groups; alkenyl/vinylpyrrolidone copolymers; graft polymers of polyolefins with maleicanhydride or vinyl imidazole; hyperbranched polyester amides;polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkylsuccinates, sorbitan monooleate, and polyisobutylene succinic anhydride.

The water clarification composition can further comprise a paraffminhibitor. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.1 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of a paraffin inhibitor, based on total weight of thecomposition. Suitable paraffin inhibitors include, but are not limitedto, paraffin crystal modifiers, and dispersant/crystal modifiercombinations. Suitable paraffin crystal modifiers include, but are notlimited to, alkyl acrylate copolymers, alkyl acrylate vinylpyridinecopolymers, ethylene vinyl acetate copolymers, maleic anhydride estercopolymers, branched polyethylenes, naphthalene, anthracene,microcrystalline wax and/or asphaltenes. Suitable paraffin dispersantsinclude, but are not limited to, dodecyl benzene sulfonate, oxyalkylatedalkylphenols, and oxyalkylated alkylphenolic resins.

The water clarification composition can further comprise a scaleinhibitor. The composition can comprise from about 0.1 wt-% to about 20wt-%, from about 0.5 wt-% to about 10 wt-%, or from about 1 wt-% toabout 10 wt-% of a scale inhibitor, based on total weight of thecomposition. Suitable scale inhibitors include, but are not limited to,phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonicacids, polyacrylamides, mono-, bis- and oligomeric phosphinosuccinicacid (PSO) derivatives, polycarboxylic acid, hydrophobically modifiedpolycarboxylic acid, salts of acrylamidomethyl propane sulfonate/acrylicacid copolymer (AMPS/AA), phosphinated maleic copolymer (PHOS/MA), andsalts of a polymaleic acid/acrylic acid/acrylamidomethyl propanesulfonate terpolymer (PMA/AA/AMPS).

The water clarification composition can further comprise an emulsifier.The composition can comprise from about 0.1 wt-% to about 10 wt-%, fromabout 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-%of an emulsifier, based on total weight of the composition. Suitableemulsifiers include, but are not limited to, salts of carboxylic acids,products of acylation reactions between carboxylic acids or carboxylicanhydrides and amines, and alkyl, acyl and amide derivatives ofsaccharides (alkyl-sacchmide emulsifiers).

The water clarification composition can further comprise a waterclarifier. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of a water clarifier, based on total weight of thecomposition. Suitable water clarifiers include, but are not limited to,inorganic metal salts such as alum, aluminum chloride, and aluminumchlorohydrate, or organic polymers such as acrylic acid-based polymers,acrylamide-based polymers, polymerized amines, alkanolamines,thiocarbamates, and cationic polymers such as diallyldimethylammoniumchloride (DADMAC).

The water clarification composition can further comprise an emulsionbreaker. The composition can comprise from about 0.1 wt-% to about 10wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% toabout 4 wt-% of an emulsion breaker, based on total weight of thecomposition. Suitable emulsion breakers include, but are not limited to,dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonicacid (NAXSA), epoxylated and propoxylated compounds, anionic, cationicand nonionic surfactants, and resins, such as phenolic and epoxideresins.

The water clarification composition can fluffier comprise a hydrogensulfide scavenger. The composition can comprise from about 1 wt-% toabout 50 wt-%, from about 1 wt-% to about 40 wt-%, or from about 1 wt-%to about 30 wt-% of a hydrogen sulfide scavenger, based on total weightof the composition. Suitable additional hydrogen sulfide scavengersinclude, but are not limited to, oxidants (e.g., inorganic peroxidessuch as sodium peroxide or chlorine dioxide); aldehydes (e.g., of 1-10carbons such as formaldehyde, glyoxal, glutaraldehyde, acrolein, ormethacrolein; triazines (e.g., monoethanolamine triazine,monomethylamine triazine, and triazines from multiple amines or mixturesthereof); condensation products of secondary or tertiary amines andaldehydes, and condensation products of alkyl alcohols and aldehydes.

The water clarification composition can further comprise a gas hydrateinhibitor. The composition can comprise from about 0.1 wt-% to about 25wt-%, from about 0.5 wt-% to about 5 wt-%, or from about 1 wt-% to about10 wt-% of a gas hydrate inhibitor, based on total weight of thecomposition. Suitable gas hydrate inhibitors include, but are notlimited to, thermodynamic hydrate inhibitors (THI), kinetic hydrateinhibitors (KHI), and anti-agglomerates (AA). Suitable thermodynamichydrate inhibitors include, but are not limited to, sodium chloride,potassium chloride, calcium chloride, magnesium chloride, sodiumbromide, formate brines (e.g. potassium formate), polyols (such asglucose, sucrose, fructose, maltose, lactose, gluconate, monoethyleneglycol, diethylene glycol, Methylene glycol, mono-propylene glycol,dipropylene glycol, tripropylene glycols, tetrapropylene glycol,monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol,diglycerol, triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)),methanol, propanol, ethanol, glycol ethers (such as diethyleneglycolmonomethylether, ethyleneglycol monobutylether), and alkyl or cyclicesters of alcohols (such as ethyl lactate, butyl lactate, methylethylbenzoate).

The water clarification composition can further comprise a kinetichydrate inhibitor. The composition can comprise from about 0.1 wt-% toabout 25 wt-%, from about 0.5 wt-% to about 20 wt-%, or from about 1wt-% to about 10 wt-% of a kinetic hydrate inhibitor, based on totalweight of the composition. Suitable kinetic hydrate inhibitors andanti-agglomerates include, but are not limited to, polymers andcopolymers, polysaccharides (such as hydroxyethylcellulose (HEC),carboxymethylcellulose (CMC), starch, starch derivatives, and xanthan),lactams (such as polyvinylcaprolactam, polyvinyl lactam), pyrrolidones(such as polyvinyl pyrrolidone of various molecular weights),surfactants (such as fatty acid salts, ethoxylated alcohols,propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters,polyglycerol esters of fatty acids, alkyl glucosides, alkylpolyglucosides, alkyl sulfates, alkyl sulfonates, alkyl estersulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amidobetaines), hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, and proteins.

The water clarification composition can further comprise a pH modifier.The composition can comprise from about 0.1 wt-% to about 20 wt-%, fromabout 0.5 wt-% to about 10 wt-%, or from about 0.5 wt-% to about 5 wt-%of a pH modifier, based on total weight of the composition. Suitable pHmodifiers include, but are not limited to, alkali hydroxides, alkalicarbonates, alkali bicarbonates, alkaline earth metal hydroxides,alkaline earth metal carbonates, alkaline earth metal bicarbonates andmixtures or combinations thereof. Exemplary pH modifiers include sodiumhydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, magnesium oxide, and magnesium hydroxide.

The water clarification composition can further comprise a surfactant.The composition can comprise from about 0.1 wt-% to about 10 wt-%, fromabout 0.5 wt-% to about 5 wt-%, or from about 0.5 wt-% to about 4 wt-%of a surfactant, based on total weight of the composition. Suitablesurfactants include, but are not limited to, anionic surfactants andnonionic surfactants. Anionic surfactants include alkyl aryl sulfonates,olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ethersulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl andethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinatesand sulfosuccinamates. Nonionic surfactants include alcohol alkoxylates,alkylphenol alkoxylates, block copolymers of ethylene, propylene andbutylene oxides, alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl)amine oxides, alkyl amidopropyl dimethyl amine oxides,alkylamidopropyl-bis(2-hydroxyethyl) amine oxides, alkyl polyglucosides,polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitanesters, and alkoyl polyethylene glycol esters and diesters. Alsoincluded are betaines and sultanes, amphoteric surfactants such as alkylamphoacetates and amphodiacetates, alkyl amphopropionates andamphodipropionates, and alkyliminodipropionate.

The water clarification composition can further comprise additionalfunctional agents or additives that provide a beneficial property. Forexample, additional agents or additives can be sequestrants,solubilizers, lubricants, buffers, cleaning agents, rinse aids,preservatives, binders, thickeners or other viscosity modifiers,processing aids, carriers, water-conditioning agents, foam inhibitors orfoam generators, threshold agents or systems, aesthetic enhancing agents(e.g., dyes, odorants, perfumes), or other additives suitable forformulation with a corrosion inhibitor composition, and mixturesthereof. Additional agents or additives will vary according to theparticular water clarification composition being manufactured and itsintend use as one skilled in the art will appreciate.

Alternatively, the water clarification composition does not contain anyof the additional water clarification composition agents or additives.

Additionally, the water clarification composition can be formulated intocompositions comprising the following components as shown in Tables1A-1B. These formulations include the ranges of the components listedand can optionally include additional agents. The values in Tables 1A-1Bbelow are weight percentages.

TABLE 1A Exemplary Water Clarification Compositions Component 1 2 3 4 56 7 8 9 10 11 12 Multiple charged 0.1-20 0.1-20 0.1-20 0.1-20 0.1-200.1-20  10-20  10-20  10-20  10-20  10-20 0.1-20 cationic or anioniccompounds Organic solvent   5-40 —   5-50 —   5-50   5-50   5-40 —  5-50 — —  10-20 corrosion inhibitor 0.1-20 0.1-20 — — — — 0.1-200.1-20 — — — 0.1-20 Additional 0.1-5 0.1-5 0.1-5 0.1-5 — — 0.1-5 0.1-50.1-5 — — 0.1-5 Coagulant/Flocculant Scale inhibitor   1-10   1-10  1-10   1-10   1-10 —   1-10   1-10   1-10   1-10 —   1-10 Dispersant —— — — — — — — — — — 0.1-25 Biocide 0.5-5 0.5-5 0.5-5 0.5-5 0.5-5 0.5-50.5-5 0.5-5 0.5-5 0.5-5 0.5-5 Water 0.00   0-40   0-10   0-60   0-15  0-25 0.00   0-40   0-10   0-65   0-75

TABLE 1B Exemplary Water Clarification Compositions Component 13 14 1516 17 18 19 20 21 22 23 24 Multiple charged 0.1-20 0.1-20 0.1-20 0.1-200.1-20 0.1-20  10-20  10-20  10-20  10-20  10-20  10-20 cationic oranionic compounds Organic solvent —  10-20 —  10-35  10-35 —  10-15 — — 10-35  10-35 — Additional corrosion 0.1-20 0.1-20 0.1-20 0.1-20 0.1-200.1-20 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 inhibitor Additional0.1-5 — — — — — 0.1-5 — — — — — Coagulant/Flocculant Scale inhibitor  1-10   1-10 — —   1-10 —   1-10   1-10 — — —   1-10 Dispersant 0.1-250.1-25 0.1-25 — — — 0.1-25 0.1-25 0.1-25 — 0.1-25 — Biocide — — — — —0.5-5 0.5-5 0.5-5 0.5-5 0.5-5 — — Water   0-20   0-5   0-35   0-25  0-15   0-55 0.00   0-20   0-30   0-20 0.00   0-50

Water System or Waste Water Source

In some embodiments, the water system in the disclosed methods herein isan industrial water system. In some embodiments, the water system is anindustrial waste water source or system. In other embodiments, the watersystem can be, but is not limited to, a cooling water system, includingan open recirculating system, closed and once-through cooling watersystem, boilers and boiler water system, petroleum well system, downholeformation, geothermal well, and other water system in oil and gas fieldapplications, a mineral washing system, flotation and benefactionsystem, paper mill digester, washer, bleach plant, stock chest, whitewater system, paper machine surface, black liquor evaporator in the pulpindustry, gas scrubber and air washer, continuous casting processes inthe metallurgical industry, air conditioning and refrigeration system,process waters, including industrial and petroleum process water,indirect contact cooling and heating water, water reclamation system,water purification system, membrane filtration water system, foodprocessing stream (meat, vegetable, sugar beets, sugar cane, grain,poultry, fruit and soybean), waste treatment system, clarifier,liquid-solid application, municipal sewage treatment, municipal watersystem, potable water system, aquifer, water tank, sprinkler system,water system used in oil refinery industry, or water heater.

In some embodiments, the water system is a cooling water system,including open recirculating, closed and once-through cooling watersystem, paper machine surface, food processing stream, waste treatmentsystem, water system used in oil refinery industry, or potable watersystem.

In some embodiments, the water system is a waste water source from afactory, residential home, industrial processing, or like. In someembodiments, the waste water source comprises oil-in-water emulsion. Insome embodiments, the waste water source is a water source comprisingsolid or liquid particles inside water.

In some embodiments, the waste water source is an oily waste water fromfood and beverage, steel, automotive, transportation, refinery,pharmaceutical, metals, paper and pulp, chemical processing, andhydrocarbon processing industries.

In other embodiments, the waste water source is an oily waste water fromfood and beverage process and water system used in oil refineryindustry. In yet some other embodiments, the waste water source is anoily waste water in oil and gas operations.

Use of the Methods or Compositions Disclosed

In some embodiments, for the methods disclosed herein, providing a waterclarification composition into a water system means that the waterclarification composition, multiple charged cationic or anioniccompounds, or a use solution thereof is added into the water system or afluid of the water system. In other embodiments, providing a waterclarification composition into a water system means adding the waterclarification composition, multiple charged cationic or anioniccompounds, or a use solution thereof to the water of the water system.In some other embodiments, providing a water clarification compositioninto a water system means adding the water clarification composition,multiple charged cationic or anionic compounds, or a use solutionthereof to a fluid which contacts or mixes with the water system. Thewater clarification composition or multiple charged cationic or anioniccompounds may be added continuously, or intermittently when morecompounds or compositions may be needed.

A use solution of a water clarification composition or one or moremultiple charged cationic or anionic compounds as used herein refers toa diluted solution for the composition or compounds by a diluent. Adiluent as used herein refers to water, the water of the water system,or one of the carriers or solvents defined herein. The waterclarification composition or the compounds can be diluted by a factor of0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11-1,000,000, or any value therebetween to generate a use solution and then provide the use solution toa water system. In this disclosure, when a composition or multiplecharged cationic or anionic compounds are applied, either thecomposition/compounds or use solution thereof is applied.

In some embodiments, the water clarification composition or multiplecharged cationic or anionic compounds may be added to the water of thewater system in an amount ranging from about 1 ppm to about 1000 ppm. Inother embodiments, the amount of the water clarification composition ormultiple charged cationic or anionic compounds in the water of the watersystem or in the waste water source may range from about 5 ppm to about100 ppm, about 5 ppm to about 75 ppm, about 5 ppm to about 50 ppm, about5 ppm to about 40 ppm, about 5 ppm to about 30 ppm, about 10 ppm toabout 60 ppm, about 10 ppm to about 50 ppm, about 10 ppm to about 40ppm, about 10 ppm to about 30 ppm, about 20 ppm to about 60 ppm, about20 ppm to about 50 ppm, about 20 ppm to about 40 ppm, or about 20 ppm toabout 30 ppm, about 25 ppm to about 75 ppm, or about 25 ppm to about 50ppm. In some embodiments, the water clarification composition ormultiple charged cationic or anionic compounds may be added to the waterto an amount ranging from about 100 ppm to about 1000 ppm, about 125 ppmto about 1000 ppm, about 250 ppm to about 1000 ppm, or about 500 ppm toabout 1000 ppm.

The water clarification composition or multiple charged cationic oranionic compounds can be used for clarifying a water system or a wastewater source in oil and gas applications such as by treating the watersystem or waste water source with an effective amount of the compound orcomposition as described herein. The compounds and compositions can beused in any industry where it is desirable to clarify a water system orwater source.

The water clarification composition or multiple charged cationic oranionic compounds can be used in a condensate/oil systems/gas system, orany combination thereof. For example, the water clarificationcomposition or multiple charged cationic or anionic compounds can beused in the water of a heat exchanger. The water clarificationcomposition or multiple charged cationic or anionic compounds can beapplied to a liquid produced, or used in the production, transportation,storage, and/or separation of crude oil or natural gas. The waterclarification composition or multiple charged cationic or anioniccompounds can be applied to a gas stream used or produced in acoal-fired process, such as a coal-fired power plant.

The water clarification composition or multiple charged cationic oranionic compounds can be applied to a liquid or waste water sourceproduced or used in a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process.

A fluid to which the water clarification composition or multiple chargedcationic or anionic compounds can be introduced can be an aqueousmedium. The aqueous medium can comprise water, gas, and optionallyliquid hydrocarbon.

A fluid to which the water clarification composition or multiple chargedcationic or anionic compounds can be introduced can be a liquidhydrocarbon. The liquid hydrocarbon can be any type of liquidhydrocarbon including, but not limited to, crude oil, heavy oil,processed residual oil, bituminous oil, coker oils, coker gas oils,fluid catalytic cracker feeds, gas oil, naphtha, fluid catalyticcracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, andkerosene. The fluid or gas can be a refined hydrocarbon product.

A fluid or gas treated with the water clarification composition ormultiple charged cationic or anionic compounds can be at any selectedtemperature, such as ambient temperature or an elevated temperature. Thefluid (e.g., liquid hydrocarbon) or gas can be at a temperature of fromabout 40° C. to about 250° C. The fluid or gas can be at a temperatureof from about −50° C. to about 300° C., from about 0° C. to about 200°C., from about 10° C. to about 100° C., or from about 20° C. to about90° C. The fluid or gas can be at a temperature of at a temperature ofabout 22° C., about 23° C., about 24° C., about 25° C., about 26° C.,about 27° C., about 28° C., about 29° C., about 30° C., about 31° C.,about 32° C., about 33° C., about 34° C., about 35° C., about 36° C.,about 37° C., about 38° C., about 39° C., or about 40° C. The fluid orgas can be at a temperature of about 85° C., about 86° C., about 87° C.,about 88° C., about 89° C., about 90° C., about 91° C., about 92° C.,about 93° C., about 94° C., about 95° C., about 96° C., about 97° C.,about 98° C., about 99° C., or about 100° C.

The water clarification composition or multiple charged cationic oranionic compounds can be added to a fluid at various levels of watercut. For example, the water cut can be from 0% to 100% volume/volume(v/v), from 1% to 80% v/v, or from 1% to 60% v/v. The fluid can be anaqueous medium that contains various levels of salinity. The fluid canhave a salinity of 0% to 25%, about 1% to 24%, or about 10% to 25%,weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas in which the water clarification composition ormultiple charged cationic or anionic compounds are introduced can becontained in and/or exposed to diverse types of apparatuses. Forexample, the fluid or gas can be contained in an apparatus thattransports fluid or gas from one point to another, such as an oil and/orgas pipeline. The apparatus can be part of an oil and/or gas refinery,such as a pipeline, a separation vessel, a dehydration unit, or a gasline. The fluid can be contained in and/or exposed to an apparatus usedin oil extraction and/or production, such as a wellhead. The apparatuscan be part of a coal-fired power plant. The apparatus can be a scrubber(e.g., a wet flue gas desulfurizer, a spray dry absorber, a dry sorbentinjector, a spray tower, a contact or bubble tower, or the like). Theapparatus can be a cargo vessel, a storage vessel, a holding tank, or apipeline connecting the tanks, vessels, or processing units.

The water clarification composition or multiple charged cationic oranionic compounds can be introduced into a fluid or gas of the watersystem by any appropriate method for ensuring dispersal through thefluid or gas. For examples, the water clarification composition ormultiple charged cationic or anionic compounds can be added to thehydrocarbon fluid before the hydrocarbon fluid contacts the surface.

The water clarification composition or multiple charged cationic oranionic compounds can be added at a point in a flow line upstream fromthe point at which water clarification is desired. The waterclarification composition or multiple charged cationic or anioniccompounds can be injected using mechanical equipment such as chemicalinjection pumps, piping tees, injection fittings, atomizers, quills, andthe like.

The water clarification composition or multiple charged cationic oranionic compounds can be pumped into an oil and/or gas pipeline using anumbilical line. A capillary injection system can be used to deliver thewater clarification composition or multiple charged cationic or anioniccompounds to a selected fluid.

A fluid to which the water clarification composition or multiple chargedcationic or anionic compounds can be introduced can be an aqueousmedium. The aqueous medium can comprise water, gas, and optionallyliquid hydrocarbon. A fluid to the water clarification composition ormultiple charged cationic or anionic compounds can be introduced can bea liquid hydrocarbon.

The water clarification composition or multiple charged cationic oranionic compounds can be introduced into a liquid and a mixture ofseveral liquids, a liquid and gas, liquid, solid, and gas. The waterclarification composition or multiple charged cationic or anioniccompounds can be injected into a gas stream as an aqueous or non-aqueoussolution, mixture, or slurry.

The fluid or gas can be passed through an absorption tower comprisingthe water clarification composition or multiple charged cationic oranionic compounds.

The water clarification composition or multiple charged cationic oranionic compounds can be applied to a fluid or gas to provide anyselected concentration. In practice, the water clarification compositionor multiple charged cationic or anionic compounds are typically added toa flow line to provide an effective treating dose of the waterclarification composition or multiple charged cationic or anioniccompounds from about 0.01 ppm to about 5,000 ppm. The waterclarification composition or multiple charged cationic or anioniccompounds can be applied to a fluid or gas to provide an activeconcentration of about 1 parts per million (ppm) to about 1,000,000 ppm,about 1 parts per million (ppm) to about 100,000 ppm, or about 10 ppm toabout 75,000 ppm. The polymer salts/compositions can be applied to afluid to provide an actives concentration of about 100 ppm to about10,000 ppm, about 200 ppm to about 8,000 ppm, or about 500 ppm to about6,000 ppm. The actives concentration means the concentration of waterclarification composition or multiple charged cationic or anioniccompounds.

The water clarification composition or multiple charged cationic oranionic compounds can be applied to a water system or a waste watersource to provide an active concentration of about 0.1 ppm, about 0.5ppm, about 1 ppm, about 2 ppm, about 5 ppm, about 10 ppm, about 20 ppm,about 100 ppm, about 200 ppm, about 500 ppm, or about 1,000 ppm. Thepolymer salts/compositions can be applied to a water system or a wastewater source to provide an actives concentration of about 0.125 ppm,about 0.25 ppm, about 0.625 ppm, about 1 ppm, about 1.25 ppm, about 2.5ppm, about 5 ppm, about 10 ppm, or about 20 ppm. Each water system orwaste water source can have its own dose level requirements, and theeffective dose level of the water clarification composition or multiplecharged cationic or anionic compounds to sufficiently reduce theturbidity of the water system or waste water source can vary with thewater system in which it is used.

The water clarification composition or multiple charged cationic oranionic compounds can be applied continuously, in batch, or acombination thereof. The water clarification composition or multiplecharged cationic or anionic compounds dosing can be continuous. Thewater clarification composition or multiple charged cationic or anioniccompounds dosing can be intermittent (e.g., batch treatment) or can becontinuous/maintained and/or intermittent.

Dosage rates for continuous treatments typically range from about 10 ppmto about 500 ppm, or about 10 ppm to about 200 ppm. Dosage rates forbatch treatments typically range from about 10 ppm to about 400,000 ppm,or about 10 ppm to about 20,000 ppm. The water clarification compositionor multiple charged cationic or anionic compounds can be applied as apill to a pipeline, providing a high dose (e.g., 20,000 ppm) of thecomposition.

The flow rate of a flow line in which the water clarificationcomposition or multiple charged cationic or anionic compounds is usedcan be between 0.1 and 100 feet per second, or between 0.1 and 50 feetper second. The water clarification composition or multiple chargedcationic or anionic compounds can also be formulated with water in orderto facilitate addition to the flow line.

The surface can be a part of a wellbore or equipment used in theproduction, transportation, storage, and/or separation of a fluid suchas crude oil or natural gas.

More specifically, the surface can be a part of equipment used acoal-fired process, a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process. Preferably, the surface can be a part of equipment usedin the production of crude oil or natural gas.

The equipment can comprise a pipeline, a storage vessel, downholeinjection tubing, a flow line, or an injection line.

The water clarification composition or multiple charged cationic oranionic compounds are useful for process or waste water source in thefood service or food processing industries.

The water clarification composition or multiple charged cationic oranionic compounds can also be used for clarifying a water system orwaste water source in other industrial process, such as those fromheaters, cooling towers, boilers, retort waters, rinse waters, asepticpackaging wash waters, and the like.

The water clarification composition or multiple charged cationic oranionic compounds can be used to treat a water or waste water sourcefrom janitorial and/or housekeeping applications, food processing, andin laundry applications.

The water clarification composition or multiple charged cationic oranionic compounds can be dispensed in any suitable method generallyknown by one skilled in the art. For example, a spray-type dispenser canbe used. A spray-type dispenser functions by impinging a water sprayupon an exposed surface of a composition to dissolve a portion of thecomposition, and then immediately directing the concentrate solutionincluding the composition out of the dispenser to a storage reservoir ordirectly to a point of use.

The water clarification composition or multiple charged cationic oranionic compounds can be dispensed by immersing either intermittently orcontinuously into the water, fluid, or gas of the water system. Thewater clarification composition or multiple charged cationic or anioniccompounds can then dissolve, for example, at a controlled orpredetermined rate. The rate can be effective to maintain aconcentration of the dissolved compounds or compositions that areeffective for use according to the methods disclosed herein.

The water clarification composition disclosed herein can comprise fromabout 10 wt-% to about 90 wt-% of the carrier, biocide, corrosioninhibitor, additional water clarification composition agent, acombination thereof and from about 10 wt-% to about 90 wt-% of one ormore multiple charged cationic or anionic compounds, from about 20 wt-%to about 80 wt-% of the carrier, biocide, corrosion inhibitor,additional water clarification composition agent, a combination thereofand from about 20 wt-% to about 80 wt-% of one or more multiple chargedcationic or anionic compounds, from about 30 wt-% to about 70 wt-% ofthe carrier, biocide, corrosion inhibitor, additional waterclarification composition agent, a combination thereof and from about 40wt-% to about 60 wt-% of one or more multiple charged cationic oranionic compounds, or from about 1 wt-% to about 10 wt-% of the carrier,biocide, corrosion inhibitor, additional water clarification compositionagent, a combination thereof and from about 10 wt-% to about 90 wt.% ofone or more multiple charged cationic or anionic compounds.

In one aspect, disclosed herein is a water clarification composition,wherein the water clarification composition comprises a compound and oneor more additional water clarification composition agents, wherein thecompound is derived from an aza-Michael Addition Reaction between apolyamine and an activated olefm having an ionic group according to oneof the following formulas

wherein X is NH or O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2′) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; m is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H, —PO₃H,—OPO₃H, —OSO₃H, or a salt thereof; and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2 or more positive charges or multiple chargedanionic compound having 2 or more negative charges and wherein the waterclarification composition reduces turbidity of the water system.

In another aspect, disclosed here is a method of clarifying a watersystem, wherein the method comprises providing a water clarificationcomposition into a water system, wherein the water clarificationcomposition comprises a compound or its salt and one or more additionalwater clarification composition agents, wherein the compound is derivedfrom an aza-Michael Addition Reaction between a polyamine and anactivated olefin having an ionic group according to one of the followingformulas

wherein X is NH or 0; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2′) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; m is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H, —PO₃H,—OPO₃H, —OSO₃H, or a salt thereof; and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2 or more positive charges or multiple chargedanionic compound having 2 or more negative charges and wherein the waterclarification composition reduces turbidity of the water system.

The structures of and the reactions leading to the exemplary multiplecharged cationic compounds (I) using a linear polyethyleneimine is shownin FIG. 1. The scheme for preparation of exemplary cationic polymercompositions (II) using a branched polyethyleneimine is shown in FIG. 2.

In FIG. 1 and FIG. 2, k, l, m, n, o, or p is an integer of 1-100; X isNH or O; R² is H, CH₃, or an unsubstituted, linear or branched C₂-C₁₀alkyl group; R³ is absent or an unsubstituted, linear or branched C₁-C₃₀alkylene group; Y is —NR⁴R⁵R⁶⁽⁺⁾ or a salt thereof; R⁴, R⁵, and R⁶ areindependently C₁-C₁₀ alkyl group or benzyl group.

The structures I and H in FIG. 1 and FIG. 2 are depiction of generalizedand exemplary reaction products. In structures I and H, all thesecondary and primary amines in the polyethyleneimine react with theactivated olefins so that no secondary amines remain. It is possiblethat in the disclosed multiple charged cationic or anionic compounds,some secondary or primary amine groups do not react completely with theactivated olefins and remain as primary or secondary amines in multiplecharged cationic or anionic compounds or their salts.

In some embodiments, the polyamine is NH₂—[R^(10′)]_(n)—NH₂,(RNH)_(n)—RNH₂, H₂N—(RNH)_(n)—RNH₂, or H₂N—(RN(R′))_(n)—RNH₂, whereinR^(10′) is a linear or branched, unsubstituted or substituted C₂-C₁₀alkylene group, or combination thereof; R is —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted orsubstituted C₄-C₁₀ alkylene group, or combination thereof; R′ is —CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstitutedor substituted C₄-C₁₀ alkyl group, RNH₂, RNHRNH₂, or RN(RNH₂)₂; and ncan be from 2 to 1,000,000. The monomer in a polyamine, e g , the R orR′ group, can be the same or different. In this disclosure, a polyaminerefers to both small molecule polyamine when n is from 1 to 9 andpolymeric polyamine when n is from 10 to 1,000,000.

In other words, the multiple charged cationic or anionic compounds canbe one having the generic formula of NA₂-[R^(10′)]_(n)-NA₂,(RNA)_(n)—RNA₂, A₂N—(RNA)_(n)—RNA₂, or A₂N—(RN(R′))_(n)—RNA₂, whereinR^(10′) is a linear or branched, unsubstituted or substituted C₂-C₁₀alkylene group, or combination thereof; R is —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted orsubstituted C₄-C₁₀ alkylene group, or combination thereof; R′ is —CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstitutedor substituted C₄-C₁₀ alkyl group, RNA₂, RNARNA₂, or RN(RNA₂)₂; n can befrom 2 to 1,000,000; A is H or

or one of H,

or a combination thereof, each of the compounds contain at least 2non-proton and cationic or anionic A groups, at least 3 non-proton andcationic or anionic A groups, at least 4 non-proton and cationic oranionic A groups, at least 5 non-proton and cationic or anionic Agroups, or more than 6 and cationic or anionic A groups. In someembodiments, A is H or positively charged

In some other embodiments, A is H or negatively

charged

In some embodiments, at least two of the primary NH₂ protons are

and the rest of primary NH₂ protons remains. In some embodiments, atleast two of the primary NH₂ protons are

and the rest of primary NH₂ protons remains. In some other embodiments,all of the primary NH₂ protons are replaced by

In some embodiments, some of primary NH₂ and secondary NH proton arereplaced by

In some embodiments, all of primary NH₂ and some of secondary NH protonare replaced by

In some embodiments of the disclosed compounds herein, X is NH. In someother embodiments, X is O.

In some embodiments, R² is H. In some embodiments, R² is CH₃. In yetsome other embodiments, R² is CH₃CH₃, CH₂CH₂CH₃, or CH(CH₃)₂.

In some embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾. In some other embodiments, Y is—NR₄R₅R₅ ⁽⁺⁾, and R⁴, R⁵, and R⁶ are independently CH₃. In yet someother embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾, and R⁴ and R⁵, independently CH₃,and R⁶ is a C₂-C₁₂ aromatic alkyl. In some other embodiments, Y is—NR₄R₅R₆ ⁽⁺⁾, and R⁴ and R⁵, independently CH₃, and R⁶ is —CH₂—C₆H₆.

In some embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾ and the counter ion for Y anynegative charged ion or species. In some other embodiments, the counterion for Y is chloride, bromide, fluoride, iodide, acetate, al urinate,cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate,carbonate, hydrogen carbonate, hydrogen oxalate, hydrogen sulfate,hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

In some embodiments, Y′ is —COOH or salt thereof. In some otherembodiments, Y′ is —SO₃H, —OSO₃H or salt thereof. In yet some otherembodiments, Y′ is —OPO₃H, —PO₃H, or salt thereof. In some otherembodiments, Y′ is an acidic species or salt thereof.

In some embodiments, R³ is CH₂. In some other embodiments, R³ is CH₂CH₂.In other embodiments, R³ is C(CH₃)₂. In yet some other embodiments, R³is an unsubstituted, linear, and saturated C₁-C₁₀ alkylene group. Insome embodiments, R³ is an unsubstituted, linear, and unsaturated C₁-C₁₀alkylene group.

In some embodiments, R³ is a linear C₈-C₁₈ alkyl, alkenyl, or alkynylgroup. In some other embodiments, R³ is a branched C₈-C₂₀ alkyl,alkenyl, or alkynyl group.

In some embodiments, the polyamine is a linear, branched, or dendrimerpolyamine with a general formula of —[RNH]_(n)—, wherein R is —CH₂CH₂—,—CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted orsubstituted C₄-C₁₀ alkylene group, or combination thereof and n is aninteger of 3, 4, 5, 6, 7-9, or 10 to 1,000,000.

In some embodiments, the polyamine is a linear, branched, or dendrimerpolyamine with a general formula of (RNH)_(n)—RNH₂, wherein R is —CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstitutedor substituted C₄-C₁₀ alkylene group, or combination thereof and n canfrom 2 to 1,000,000. In some embodiments, R is the same in each monomer.In some other embodiments, R can be different from one monomer toanother monomer.

In some other embodiments, the polyamine is a linear, branched, ordendrimer polyamine with a general formula of H₂N—(RNH)_(n)—RNH₂,wherein R is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear orbranched, unsubstituted or substituted C₄-C₁₀ alkylene group, orcombination thereof and n can be from 2 to 1,000,000. In someembodiments, R is the same in each monomer. In some other embodiments, Rcan be different from one monomer to another monomer.

In yet some other embodiments, the polyamine is a linear, branched, ordendrimer polyamine with a general formula of H₂N—(RN(R′))_(n)—RNH₂,wherein R is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear orbranched, unsubstituted or substituted C₄-C₁₀ alkylene group, orcombination thereof; R′ is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, alinear or branched, unsubstituted or substituted C₄-C₁₀ alkyl group,RNH₂, RNHRNH₂, or RN(RNH₂)₂; and n can be from 2 to 1,000,000. In someembodiments, R or R′ is the same in each monomer. In some otherembodiments, R or R′ can be different from one monomer to anothermonomer.

In some embodiments, the polyamine is one with a general formula ofNH₂—[R^(10′)]_(n)—NH₂, wherein R^(10′) is a linear or branched,unsubstituted or substituted C₄-C₁₀ alkylene group, or combinationthereof and n is an integer of 3, 4, 5, 6, 7-9, or 10 to 1,000,000. Insome other embodiments, R^(10′) can be different from one monomer toanother monomer.

In some embodiments, the polyamine is one or more of polyamines underJEFFAMINE® by Huntsman.

In some embodiments, the polyamine is an unmodified polyamine. In someother embodiments, the polyamine is a modified polyamine. As usedherein, a “modified polyamine” refers to a polyamine in which one ormore NH protons is substituted by a non-proton group, such as an alkyl.

In yet some embodiments, the polyamine is an ethoxylated polyamine,propylated polyamine, polyamine with polyquat, polyamine withpolyglycerol, or combination thereof.

In some embodiments, the polyamine is diamine or triamine having anaverage molecular weight (M_(w)) of from about 130 to about 4,000.

In yet some other embodiments, the polyamine is a linear, branched, ordendrimer polyethyleneimine. In some other embodiments, the polyaminecomprises only primary and secondary amine groups. In some embodiments,the polyamine comprises only primary, secondary, and tertiary aminegroups. In some other embodiments, the polyamine comprises only primaryand tertiary amine groups.

In some embodiments, the polyamine is a single compound. In some otherembodiments, the polyamine is a mixture of two or more differentpolyamines, wherein the different polyamines have different molecularweight, different structure, or both.

In some embodiments, the polyamine has an average molecular weight(M_(w)) of from about 130 to about 2,000,000 Da. In some otherembodiments, the polyamine has an average molecular weight (M_(w)) offrom about 130 to about 5,000 Da. In yet some other embodiments, thepolyamine has an average molecular weight (M_(w)) of from about 130 toabout 25,000 Da.

In some embodiments, the polyamine has an average molecular weight(M_(w)) of about 60-200, about 100-400, about 100-600, about 600-5,000,about 600-800, about 800-2,000, about 800-5,000, about 100-2,000,000,about 100-25,000, about 600-25,000, about 800-25,000, about 600-750,000,about 800-750,000, about 25,000-750,000, about 750,000-2,000,000, about100, about 200, about 300, about 400, about 500, about 600, about 700,about 800, about 1,000, about 1,500, about 2,000, about 3,000, about5,000, about 8,000, about 10,000, about 15,000, about 20,000, about50,000, about 100,000, about 250,000, about 500,000, about 1,000,000,2,000,000, or any value there between.

In some embodiments, the compound is a mixture derived from a linearpolyethyleneimine and (3-Acrylamidopropyl)trimethylammonium chloride(APTAC). In some other embodiments, the compound is a mixture derivedfrom a linear polyethyleneimine and[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC).

In some other embodiments, the multiple charged cationic or anioniccompound is a mixture derived from a branched polyethyleneimine and3-Acrylamidopropyl)trimethylammonium chloride (APTAC). In some otherembodiments, the compound is a mixture derived from a linearpolyethyleneimine and [3-(Methacryloylamino)propyl]trimethylammoniumchloride (MAPTAC).

In some embodiments, the activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methylsulfate (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethanaminiumchloride (DMAEA-MSQ).

In some other embodiments, the activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), ormixture thereof.

In some other embodiments, the activated olefin is2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methylsulfate (DMAEA-MSQ), 2-(acryloyloxy)-N,N,N-trimethylethanaminiumchloride (DMAEA-MSQ), or mixture thereof.

In some embodiments, the activated olefin is acrylic acid, methacrylicacid, itaconic acid, maleic acid, vinylsulfonic acid, viuylphosphonicacid, or mixture thereof.

In some other embodiments, the activated olefin is2-acrylamido-2-methylpropane sulfonic acid (AMPS),3-(allyloxy)-2-hydroxypropane-1-sulfonate, or mixture thereof.

In some other embodiments, wherein the activated olefin is vinylsulfonicacid, vinylphosphonic acid, or mixture thereof.

In yet some other embodiments, when the activated olefin containsanionic group that can bear negative charge at an alkaline pH, thecounter positive ions for the negative charges include, but are notlimited to, alkali metal ions, Li⁺, Na⁺, K⁺, NH₄ ⁺, a quaternaryammonium ion, etc.

In some embodiments, the compound is an aza-Michael Addition reactionproduct of (3-Acrylamidopropyl) trimethylammonium chloride (APTAC) andtetraethylenepentamine, E-100 (a mixture of tetraethylenepentamine(TEPA), pentaethylenehexamine (PEHA), and hexaethyleneheptamine (HEHA)),Pentaethylenehexamine (PEHA), or diethylenetriamine (DETA),respectively.

In some embodiments, the compound is an aza-Michael Addition reactionproduct of (3-Acrylamidopropyl) trimethylammonium chloride (APTAC) and apolyethylenimine with an average molecular weight (M_(w)) of about1,300, a polyethylenimine with an average molecular weight (M_(w)) ofabout 5,000, a polyethylenimine with an average molecular weight (M_(w))of about 25,000, or a polyethylenimine with an average molecular weight(M_(w)) of about 750,000, respectively.

In some embodiments, the compound is one or more of

wherein n=0-1000. It should be understood that when n is greater than 2,the compound can be a mixture of more than two cationic compounds, whichdiffer from each other by the exact locations of NH replacements.

In some other embodiments, wherein the compound is

In some other embodiments, the compound is

In some other embodiments, wherein the compound is

In some embodiments, the multiple charged cationic or anionic compoundhas an average molecular weight (M_(w)) of from about 100 to about2,000,000 Da. In some other embodiments, the multiple charged cationicor anionic compound has an average molecular weight (M_(w)) of fromabout 100 to about 50,000 Da. In yet some other embodiments, themultiple charged cationic or anionic compound has an average molecularweight (M_(w)) of from about 100 Da to about 600 Da, from about 100 Dato about 1,000 Da, from about 100 Da to about 1,400 Da, from about 100Da to about 3,000 Da, from about 100 Da to about 5,500 Da, or from about100 Da to about 10,000 Da, from about 100 Da to about 20,000 Da, fromabout 100 Da to about 30,000 Da, or from about 100 Da to about 40,000Da.

In some embodiments, the multiple charged cationic compound has at least2, at least 3, at least 4, at least 5, at least 6, at least 7, at least8, at least 9, or at least 10 positive charges. In some otherembodiments, the compound has from 10 to 1,000 positive charges, or anyvalue there between positive charges.

In some embodiments, the multiple charged cationic compound has at least2, at least 3, at least 4, at least 5, at least 6, at least 7, at least8, at least 9, or at least 10 negative charges. In some otherembodiments, the compound has from 10 to 1,000 positive charges, or anyvalue there between negative charges.

In some embodiments, the compound is soluble or dispersible in water.

In some embodiments, the water clarification composition furthercomprises a carrier. In some embodiments, the carrier is the carrier iswater, an organic solvent, or a mixture thereof.

In some embodiments, the carrier is an organic solvent. In some otherembodiments, the carrier is a mixture of an organic solvent and water.

In some embodiments, the organic solvent is an alcohol, a hydrocarbon, aketone, an ether, an alkylene glycol, a glycol ether, an amide, anitrile, a sulfoxide, an ester, or any combination thereof. In someother embodiments, the organic solvent is an alcohol, an alkyleneglycol, an alkyleneglycol alkyl ether, or a combination thereof. In yetsome embodiments, the organic solvent is methanol, ethanol, propanol,isopropanol, butanol, isobutanol, monoethyleneglycol, ethyleneglycolmonobutyl ether, or a combination thereof.

In some embodiments, the organic solvent is methanol, ethanol, propanol,isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol,2-butoxyethanol, methylene glycol, ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, diethyleneglycol monomethyl ether,diethylene glycol monoethyl ether, ethylene glycol monobutyl ether,ethylene glycol dibutyl ether, pentane, hexane, cyclohexane,methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene,heavy aromatic naphtha, cyclohexanone, diisobutylketone, diethyl ether,propylene carbonate, N-methylpyrrolidinone, N,N-dimethylformamide, amixture thereof with water, or any combination thereof.

In some embodiments, wherein the water clarification composition furthercomprises one or more of corrosion inhibitors. In some embodiments,wherein the water clarification composition further comprises one ormore of corrosion inhibitors and a carrier. In some embodiments, thecorrosion inhibitor is an imidazoline compound, a pyridinium compound,or a combination thereof.

In some embodiments, the water clarification composition furthercomprises an additional water clarification composition agent.

In some embodiments, the additional water clarification agent is anotherclarification agent. The additional clarification agent can be aninorganic coagulant. The inorganic coagulant includes, but is notlimited to, aluminum sulfate, aluminum chloride, ferric sulfate andferric chloride. In some embodiments, from about 200 to about 500 ppm ofthe inorganic coagulant can be added to the water system.

In some embodiments, the additional coagulant/flocculant agent isanother polymeric cationic, anionic, nonionic, or inorganiccoagulant/flocculant agent. In some embodiments, the additionalcoagulant/flocculant has an average molecular weight (M_(w)) of fromabout 100,000 Da to about 2,000,000 Da. In some embodiments, theadditional coagulant/flocculant has an average molecular weight (M_(w))of from about 1,000 Da to about 100,000 Da. In some embodiments, theadditional coagulant/flocculant has an average molecular weight (M_(w))of from 100,000 to 2,000,000 Da. In some embodiments, the additionalcoagulant/flocculant has an average molecular weight (M_(w)) of from2,000 to 1,000,000 Da. In some embodiments, the additionalcoagulant/flocculant has an average molecular weight (M_(w)) of from5,000 to 2,000,000 Da. In some embodiments, the additionalcoagulant/flocculant agent has an average molecular weight (M_(w)) offrom 10,000 to 100,000 Da.

In some embodiments, the additional cationic coagulant/flocculant hasnet charges of from 10 to 1,000. In some other embodiments, the additionanionic coagulant/flocculant agent has net charges of from 10 to 1,000.

In some embodiments, the additional water clarification agents includecondensation polymers as well as polymers derived from vinyl monomers.Vinyl polymers having water solubility and cationic characteristicsinclude modified polyacrylamides, modification being made, for example,by the typical Mannich reaction products or the quaternized Mannichreaction products, or other vinylic polymers that use as a vinyl monomerthose monomers containing cationic groups. Representative vinyl monomersinclude allylamine, dimethylaminoethylmethacrylate,dimethylaminoethylmethacrylate quaternized with dimethyl Sulfate,diallylcyclohexylamine hydrochloride, diallyl dimethyl ammoniumchloride, dimethyl aminoethyl acrylate and/or its acid salts,ethacrylamidopropyl trimethyl ammonium chloride, 1-acrylamido-4-methylpiperazine (quaternized with MeCl, MeBr, or dimethyl Sulfate),diethylaminoethyl acrylate and/or its acid Salts, diethylaminoethylmethacrylate and/or its acid salts, dimethylaminoethyl acrylamide and/orits acid salts, dimethylaminoethyl methacrylamide and/or its acid salts,diethyl aminoethyl acrylamide and/or its acid salts, diethyl aminoethylmethacrylamide and/or its acid Salts, and the like, and mixturesthereof. These cationic coagulants preferably have a molecular weight offrom about 2,000 to greater than about 1,000,000.

In some other embodiments, the additional water clarification agentsinclude cationic coagulants comprising polydiallyl dimethyl ammoniumchloride and one or more anionic monomers that are disclosed in U.S.Pat. Nos. 4,715,962, 5,013,456 and 5,207,924, which are incorporatedherein by reference.

In some other embodiments, the additional water clarification agentsinclude cationic coagulants comprising dimethyl ammonium chloride andVinyltrialkoxysilane monomer units that are disclosed in U.S. Pat. No.5,589,075, which are incorporated herein by reference.

In yet some other embodiments, the additional water clarification agentsinclude low molecular weight cationic coagulants, which can beepichlorohydrin-dimethylamine and polydiallyldimethylammonium chloridethat are disclosed in U.S. Pat. No. 4,655,934, which is incorporatedherein by reference.

In some embodiments, from about 1 ppm to about 50 ppm of the additionalwater clarification agent is added to the water system.

In some embodiments, the water clarification composition furthercomprises a biocide. In some embodiments, the water clarificationcomposition further comprises a biocide and carrier. In some otherembodiments, the water clarification composition further comprises abiocide, corrosion inhibitor, and carrier.

In some other embodiments, the biocide is chlorine, hypochlorite, ClO₂,bromine, ozone, hydrogen peroxide, peracetic acid, peroxycarboxylicacid, peroxycarboxylic acid composition, peroxysulphate, glutaraldehyde,dibromonitrilopropionamide, isothiazolone, terbutylazine, polymericbiguanide, methylene bisthiocyanate, tetrakis hydroxymethyl phosphoniumsulphate, and any combination thereof.

In some embodiments, the water clarification composition furthercomprises an organic sulfur compound. In some other embodiments, whereinthe organic sulfur compound is a mercaptoalkyl alcohol, mercaptoaceticacid, thioglycolic acid, 3,3′-dithiodipropionic acid, sodiumthiosulfate, thiourea, L-cysteine, tert-butyl mercaptan, sodiumthiosulfate, ammonium thiosulfate, sodium thiocyanate, ammoniumthiocyanate, sodium metabisulfite, or a combination thereof.

In some embodiments, the water clarification composition furthercomprises an acid. In some embodiments, the water clarificationcomposition further comprises an inorganic acid, mineral acid, organicacid, or mixture thereof. In some embodiments, the water clarificationcomposition comprises from about 1 wt-% to about 20 wt-% of the acid.

In some embodiments, the acid is hydrochloric acid, hydrofluoric acid,citric acid, formic acid, acetic acid, or mixture thereof.

In some embodiments, the water clarification composition furthercomprises a hydrogen sulfide scavenger. In some other embodiments, thehydrogen sulfide scavenger is an oxidant, inorganic peroxide, sodiumperoxide, chlorine dioxide; a C₁-C₁₀ aldehyde, formaldehyde, glyoxal,glutaraldehyde, acrolein, or methacrolein, a triazine, monoethanolaminetriazine, monomethylamine triazine, or a mixture thereof.

In some embodiments, the water clarification composition furthercomprises a surfactant. In some embodiments, the water clarificationcomposition further comprises a surfactant, biocide, and carrier.

In some embodiments, the surfactant is a nonionic, semi-nonionic,cationic, anionic, amphoteric, zwitterionic, Gemini, di-cationic,di-anionic surfactant, or mixtures thereof.

In some embodiments, the surfactant is an alkyl phenol, fatty acid, ormixture thereof.

In some embodiments, the water clarification composition furthercomprises an asphaltene inhibitor, a paraffin inhibitor, a scaleinhibitor, a gas hydrate inhibitor, a pH modifier, or any combinationthereof.

In some embodiments, the water clarification composition furthercomprises an emulsion breaker, reverse emulsion breaker,coagulant/flocculant agent, an emulsifier, a water clarifier, adispersant, antioxidant, polymer degradation prevention agent,permeability modifier, foaming agent, antifoaming agent, emulsifyingagent, scavenger agent for CO₂, and/or O₂, gelling agent, lubricant,friction reducing agent, salt, or mixture thereof.

In some embodiments, the water clarification composition is a liquid,gel, or a mixture comprising liquid/gel and solid.

In some embodiments, the water clarification composition or a usesolution thereof has a pH of from about 2 to about 11.

In some embodiments, the water clarification composition comprises fromabout 20 wt-% to about 60 wt-% of the compound or mixture thereof.

In some embodiments, the compound, or modified compound, or mixturethereof has a concentration of from about 1 ppm to about 1000 ppm in thetreated water system or waste water source.

In some embodiments, the water clarification composition is provided tothe water system independently, simultaneously, or sequentially with anadditional water clarification composition agent.

In some embodiment, the water system is a waste water source from afactory, residential home, industrial processing, or like. In someembodiments, the waste water source comprises oil-in-water emulsion.

In some embodiments, the water system is an oily waste water source fromfood and beverage, steel, automotive, transportation, refinery,pharmaceutical, metals, paper and pulp, chemical processing, watersystem used in oil refinery industry, or hydrocarbon processingindustries.

In some embodiments, the water system or waste water source comprisesfresh water, recycled water, salt water, surface water, produced water,or mixture thereof. In some embodiments, the water system is a coolingwater system or boiler water system.

In some other embodiments, the water system or waste water source is aone from petroleum wells, downhole formations, geothermal wells, mineralwashing, flotation and benefaction, papermaking, gas scrubbers, airwashers, continuous casting processes in the metallurgical industry, airconditioning and refrigeration, water reclamation, water purification,membrane filtration, food processing, clarifiers, municipal sewagetreatment, municipal water treatment, or potable water system.

In other embodiments, the waste water source is an oily waste water fromfood and beverage process or water system used in oil refinery industry.In yet some other embodiments, the waste water source is an oily wastewater in oil and gas operations.

In some embodiments, the water clarification composition or multiplecharged cationic or anionic compounds disclosed herein can clarify awater system as indicated by a jar test described in the Examplessection of this disclosure, when the water system or a waste watersource has a multiple charged cationic or anionic compound, or mixturethereof concentration of from about 1 ppm to about 1,000 ppm, from about1 ppm to about 900 ppm, from about 1 ppm to about 800 ppm, from about 1ppm to about 700 ppm, from about 1 ppm to about 600 ppm, from about 1ppm to about 500 ppm, from about 1 ppm to about 400 ppm, from about 1ppm to about 300 ppm, from about 1 ppm to about 250 ppm, from about 1ppm to about 200 ppm, from about 1 ppm to about 150 ppm, from about 1ppm to about 100 ppm, from about 1 ppm to about 50 ppm, from about 1 ppmto about 25 ppm, from about 1 ppm to about 10 ppm, from about 0.5 ppm toabout 2 ppm, about 950 ppm, about 850 ppm, about 750 ppm, about 650 ppm,about 550 ppm, about 450 ppm, about 350, about 250 ppm, about 150 ppm,about 50 ppm, about 25 ppm, about 10 ppm, about 5 ppm, about 2 ppm,about 1 ppm, about 0.5 ppm, or any value or range there between, afterdosing the water system or the waste water source with the multiplecharged cationic or anionic compound or mixture thereof, or the waterclarification composition.

In some embodiments, the water clarification composition can furthercomprise a surfactant. The surfactant is a nonionic, semi-nonionic,anionic, cationic, amphoteric, zwitterionic, Gemini surfactant, orcombinations thereof.

In some embodiments, the water clarification composition are solidcompositions. In some other embodiments, the water clarificationcompositions are liquid.

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

The term “weight percent,” “wt-%”, “percent by weight”, “% by weight”,and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent”, “%”, and the like are intended to be synonymous with“weight percent”, “wt-%”, etc.

The methods and compositions of the present disclosure may comprise,consist essentially of, or consist of the components and ingredients ofthe disclosed compositions or methods as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods and compositions may include additional steps, components oringredients, but only if the additional steps, components or ingredientsdo not materially alter the basic and novel characteristics of theclaimed methods and compositions.

EXAMPLES

Embodiments of the present disclosure are further defined in thefollowing non-limiting Examples. These Examples, while indicatingcertain embodiments of the disclosure, are given by way of illustrationonly. From the above discussion and these Examples, one skilled in theart can ascertain the essential characteristics of this disclosure, andwithout departing from the spirit and scope thereof, can make variouschanges and modifications of the embodiments of the disclosure to adaptit to various usages and conditions. Thus, various modifications of theembodiments of the disclosure, in addition to those shown and describedherein, will be apparent to those skilled in the art from the foregoingdescription. Such modifications are also intended to fall within thescope of the appended claims.

Example 1 Synthesis of Compound 1

(3-Acrylainidopropyl) trimethylammonium chloride (APTAC, 75%, 96 grams)and water (20 grams) were charged into a 250-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Tetraethylenepentamine (TEPA, 12 grams) was then added to thewell-stirred reaction mixture at room temperature. Reaction temperaturewas raised to 80° C. and stirred overnight or until the >98% consumptionof APTAC. The progression of reaction was monitored by ESI-MS and/or NMRspectroscopy for consumption of the monomer. The resulting aqueoussolution of Compound 1 was used as-is for its application testing.

Example 2 Synthesis of Compound 2

Ethyleneamine E-100 from Huntsman was used for this reaction. E-100 is amixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA),hexaethyleneheptamine (HEHA), and other higher molecular weight amines.E-100 is a complex mixture of various linear, cyclic, and branchedamines with a number-average molecular weight (M_(n)) of 250-300 g/mole.

(3-Aciylamidopropyl) trimethylammonium chloride (APTAC, 75%, 60 grams)and water (20 grams) were charged into a 250-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Ethyleneamine E-100 (12 grams) was then added to the well-stirredreaction mixture at room temperature. Reaction temperature was raised to80° C. and stored overnight or until the >98% consumption of APTAC. Theresulting aqueous solution of Compound 2 was used as-is for applicationtesting.

Example 3 Synthesis of Compound 3

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 70 grams)and water (20 grams) were charged into a 250-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Pentaethylenehexamine (PEHA, 10 grams, 99%) was then added to thewell-stirred reaction mixture at room temperature. Reaction temperaturewas raised to 80° C. and stirred overnight or until the >98% consumptionof APTAC. The resulting aqueous solution of Compound 3 was used as-isfor application testing.

Example 4 Synthesis of Compound 4

BASF Lupasol® G20 (50% aqueous solution of polyethylenimine with aweight-average molecular weight (M_(w)) around 1,300 g/mole) was usedfor this reaction.

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 78.55grams) was charged into a 250-mL three-necked RBF equipped with magneticstir bar, temperature probe, and condenser. Lupasol G20 (50%, 50 grams)was then added to the well-stirred reaction mixture at room temperature.Reaction temperature was raised to 80° C. and stirred overnight or untilthe >98% consumption of APTAC. The resulting aqueous solution ofCompound 4 was used as-is for application testing.

Example 5 Synthesis of Compound 5

BASF Lupasol® G100 (50% aqueous solution of a polyethyleneimine with aweight-average molecular weight (Mw) around 5000 g/mole) was used forthis reaction.

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 72.4 grams)was charged into a 250-mL three-necked RBF equipped with magnetic stirbar, temperature probe, and condenser. Lupasol G100 (50%, 50 grams) wasthen added to the well-stirred reaction mixture at room temperature.Reaction temperature was raised to 80° C. and stirred overnight or untilthe >98% consumption of APTAC. The resulting aqueous solution ofCompound 5 was used as-is for application testing.

Example 6 Synthesis of Compound 6

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 130 grams)and water (20 grams) were charged into a 250-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Diethylenetriamine (DETA, 10 grams) was then added to the well-stirredreaction mixture at room temperature. Reaction temperature was raised to80° C. and stirred overnight or until the >98% consumption of APTAC.Reaction temperature was raised to 80° C. and stirred overnight or untilthe >98% consumption of APTAC. The resulting aqueous solution ofCompound 6 was used as-is for application testing.

Example 7 Synthesis of Compound 7

BASF Lupasol® PS (33% aqueous solution of a polyethyleneimine with aweight-average molecular weight (M_(w)) around 750,000 g/mole) was usedfor this reaction.

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 250 grams)and water (80 grams) were charged into a 500-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Lupasol G100 (50%, 50 grams) was then added to the well-stirred reactionmixture at room temperature. Reaction temperature was raised to 85° C.and stirred overnight or until the >98% consumption of APTAC. Theresulting aqueous solution of Compound 7 was used as-is for applicationtesting.

Example 8 Synthesis of Compound 8

Polyethylenimine, branched (from Sigma Aldrich, with a weight-averagemolecular weight (M_(w)) around 25,000 g/mole) was used for thisreaction.

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 100 grams)and water (15 grams) were charged into a 500-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Polyethylenimine (100 grams) was then added to the well-stirred reactionmixture at room temperature. Reaction temperature was raised to 85° C.and stirred overnight or until the >98% consumption of APTAC. Theresulting aqueous solution of Compound 8 was used as-is for applicationtesting.

Example 9 Using Exemplary Multiple Charged Cationic Compounds for WaterClarification

In this Example, various exemplary multiple charged cationic compoundswere tested for clarifying three exemplary waste water systems, asynthetic water oily water mixture and two waste water systems collectedfrom two different oil refinery facilities, and compared with anincumbent compound for their water clarification effectiveness.

Fluids can contain suspended solid matter consisting of particles ofmany varied sizes. While some suspended material will be large enoughand heavy enough to settle rapidly to the bottom of the container if aliquid sample is left to stand (the settable solids), very smallparticles will settle only very slowly or not at all if the sample isregularly agitated or the particles are colloidal. These small solidparticles cause the liquid to appear turbid.

Turbidity is the cloudiness or haziness of a fluid caused by largenumbers of individual particles that are generally invisible to thenaked eye, like smoke in air. The measurement of turbidity is a key testof water quality.

The propensity of particles to scatter a light beam focused on them isnow considered a more meaningful measure of turbidity in water.Turbidity measured this way uses an instrument called a nephelometerwith the detector set up to the side of the light beam. More lightreaches the detector if there are lots of small particles scattering thesource beam than if there are few. The units of turbidity from acalibrated nephelometer are called Nephelometric Turbidity Units (NTU).To some extent, how much light reflects for a given number ofparticulates is dependent upon properties of the particles like theirshape, color, and reflectivity. For this reason (and the reason thatheavier particles settle quickly and do not contribute to a turbidityreading), a correlation between turbidity and total suspended solids(TSS) is somewhat unusual for each location or situation.

The synthetic oily water solution used in this Example was prepared asdescribed in the following manner:

-   a) Take 10L of a cold tap water in a bucket and adjust the pH to 5.0    with sulfuric acid.-   b) Add 3 mL ppm oleic acid into the cold tap water for a proximately    300 ppm oil in water mixture and emulsify the mixture at 10,000 RPM    for 2 mins.-   c) Add about 3 mL triglyceride into the mixture for a proximately    300 ppm triglyceride solution and emulsify the mixture at 10,000 RPM    for 2 mins-   d) Adjust the final pH of the solution to 8 with a caustic agent.

To determine the effectiveness of a water clarification compositionagent at improving clarity of an oily waste water, a so-called jar testwas performed as described below.

-   a) 200 mL aliquots of the synthetic aqueous solution prepared as    described above were transferred to beakers (jars).-   b) Each jar was spiked with different dosages of a test    clarification agent, so the agent concentration in each jar was 10,    15, 25, 35, 50 and 60 ppm, respectively.-   c) The mixture in each jar was mixed by a mixer for 1 min at 250 rpm    and then for 2 min at 50 rpm.-   d) Turbidities of the supernatant are recorded using Hach 2100Q    portable turbidimeter, after 20 mins of settling.

Table 2 lists the structures of the exemplary multiple charged cationiccompounds and the incumbent compound. Table 3 shows the list of namesand structures for the existing common clarification agents, which werealso tested for water clarification for comparison purposes.

Table 4 lists and FIG. 3 shows the results of the Jar Tests for threeexemplary multiple charged cationic compounds and one incumbent compoundto clarify a synthetic oily water mixture as prepared above. The resultsin Table 4 shows superior water clarity results as indicated by lowerturbidity values were obtained with the exemplary multiple chargedcationic compounds disclosed herein compared to the inline chemistryControl 1, a compound current used for water clarification.

TABLE 2 List of the structures for the tested clarification agentMultiple Charged Cationic Product Chemistry: Polyamine-APTAC adductCompound ID Polyamine activated olefin 1 Tetraethylenepentarnine (TEPA)APTAC 2 Ethyleneamine E-100 APTAC 3 Pentaethylenehexamine (PEHA) APTAC 4Lupasol ® G20 APTAC 5 Lupasol ® G100 APTAC 6 Diethylenetriamine (DETA)APTAC 7 Lupasol ® PS APTAC 8 Polyethylenimine, Mw = 25K APTAC Daltons

TABLE 3 List of the names and structures for the existing commonclarification agents Commercial Product Tested Control Compound No.Chemistry 1 Control 1 Poly(Diallyl-dimethyl-ammonium chloride) 3 Control2 Dimethylamine-Epichlorohydrin copolymer

TABLE 4 Results of the Jar Tests for three exemplaty multiple chargedcationic compounds and one incumbent compound Turbidity (NTU) atdifferent dosages Dosage in ppm and Turbidity (NTU) Compound ID 0 10 1525 35 50 60 No. 1 1000 170 192 175 172 189 197 No. 2 1000 231 261 257260 269 286 No. 3 1000 209 209 203 193 196 212 Control 1 1000 498 517525 528 534 522

The data in Table 4 and FIG. 3 also show that exemplary multiple chargedcationic compounds disclosed herein follow a similar dose responsepattern as one for the widely used 8108⁺. The data in Table 4 and FIG. 3indicates that the concentration of from above 0 ppm to about 60 ppm ofthe clarification agent is a clearly an optimum range, above which theenhanced performance is not achieved with increase in concentration.

For example, treatment of the oily solution with 10 ppm of the 8108⁺reduced its turbidity from 1000 NTU to 498 NTU, whereas 10 ppm ofCompound 1 reduced the turbidity of the same oily solution from 1000 NTUto 170 NTU. This data suggests that a significantly lower treatmentdosage of the multiple charged cationic compounds disclosed herein canbe used effectively for oily water clarification.

Table 5 shows the results after some exemplary cationic compounds andone incumbent compound was applied to a waste water system from an oilrefinery facility.

TABLE 5 Results of the Jar Tests for several exemplary multiple chargedcationic compounds and two incumbent compounds Turbidity (NTU) atVarious Concentration (ppm) Compound ID 50 ppm 100 ppm 150 ppm Control 120.3 19.6 18.4 Control 2 14.7 14.9 14.9 No. 1 12.4 11.8 11.9 No. 2 13.612.1 12.8 No. 6 11.9 11.9 12.0 No. 3 14.1 13.4 12.6 No. 5 13.8 12.4 13.3

The results in Table 5 shows that the performance differences betweenthe exemplary compounds and the incumbent compounds were not significantfor this specific waste water system. However, the exemplary compoundsare still better than the incumbent compounds.

Some exemplary compounds and one incumbent compound were tested forclarify another waste water system from another refinery facility. Table6 and FIG. 4 shows the results of the tests.

TABLE 6 Results of the Jar Tests for several exemplary multiple chargedcationic compounds and two incumbent compounds Turbidity (NTU) atVarious Concentration (ppm) Compound ID 50 150 250 300 No. 1 48.2 7665.9 97.9 No. 7 151 151 113 137 No. 8 122 115 113 120 No. 6 106 124 97.9126 Control 1 442 301 312 315

The results in Table 6 shows that the performance of the exemplarycompounds performance much better results than the incumbent compound,Control 1, for the waste water system from this specific water system.FIG. 4 shows the results of these tests as well. The results in FIG. 4show that the clarification profile for the exemplary compounds are alsodifferent from the incumbent compound and that the exemplary compoundscan achieve the turbidity reduction with a lower concentration of thecompounds. Increasing the concentration of the exemplary compounds wouldnot enhance their performances, in contrast to the incumbent compound inthe concentration range of from above 0 ppm to about 100 ppm.

Example 10 Synthesis of Compound 9

(3-Acrylamidopropyl) trimethylammonium chloride (APTAC, 75%, 100 grams)and water (20 grams) were charged into a 250-mL three-necked RBFequipped with magnetic stir bar, temperature probe, and condenser.Triethylenetetramine (TETA, 60%, 15 grams) was then added to thewell-stirred reaction mixture at room temperature. Reaction temperaturewas raised to 80° C. and stirred overnight or until the >98% consumptionof APTAC. The resulting aqueous solution of Compound 9 was used as-isfor its application testing.

Example 11 Using Exemplary Multiple Charged Cationic Compounds for WaterClarification and Turbidity Reduction in Oil and Gas Applications

In this Example, additional exemplary multiple charged cationiccompounds were tested according to a jar test procedure set forth inExample 9 (modifications described herein). All chemicals were dosed as1% solutions and the oily water solution used in this Example wasobtained from the field—produced water from a deoiled water tank. Theuntreated water had a turbidity of 398 NUT.

To determine the effectiveness of a water clarification compositionagent at improving clarity of an oily waste water, the jar test wasperformed as described below.

-   a) 200 mL aliquots of the produced water was transferred to beakers    (jars).-   b) Each jar was spiked with different dosages of a test    clarification agent (i.e. coagulant), so the agent concentration in    each jar was 25, 50, 75, 100, 125 and 150 ppm, respectively.-   c) The mixture in each jar was mixed by a mixer for 1 min at 200 rpm    and then for 5 min at 25 rpm.-   d) Turbidities of the supernatant are recorded using Hach 2100Q    portable turbidimeter, after 20 mins of settling.

Table 7 lists the structures of the exemplary multiple charged cationiccompounds and the incumbent compound evaluated in this Example. TheCompound 9 was added compared to other Compounds and Control 2 as shownin Table 7.

TABLE 7 List of the structures for the tested clarification agentMultiple Charged Cationic Product Chemistry: Polyamine-APTAC adductCompound ID Polyamine activated olefin 1 Tetraethylenepentamine (TEPA)APTAC 3 Pentaethylenehexamine (PEHA) APTAC 4 Lupasol ® G20 APTAC 5Lupasol ® G100 APTAC 9 Triethylenetetramine (TETA) APTAC Control 2Dimethylamine-Epichlorohydrin copolymer

TABLE 8 Results of the Jar Tests for exemplary multiple charged cationiccompounds and one incumbent compound (Control) Turbidity (NTU) atdifferent dosages Dosage in ppm and Turbidity (NTU) Compound ID 25 50 75100 125 150 Control 2 414 417 123 25 9 9 1 26 26 22 20 22 24 9 32 25 2423 32 26 4 119 25 23 20 25 22 3 29 22 22 20 20 20 5 405 61 23 16 16 20

The results of Table 8 suggest the following dosages are needed toclarify the evaluated produced water, as shown in Table 9.

TABLE 9 Exemplary dosages % Product Actives Chemical Actives dose dose8105 55 100 55 (Control) 1 82 25 20 3 83 25 20 9 83 25 20 4 67 50 38 568 75 51

The results demonstrate a beneficial reduction in dosage for themultiple charged cationic compounds compared to the Control, as shown inTable 10.

TABLE 10 Exemplary dosage reductions compared to Control Dose reductionChemical (%) 1 54 3 54 9 54 4 31 5 7

The above specification provides a description of the waterclarification compositions and methods of using the water clarificationcompositions for water clarification in a water system. It will beobvious that the same may be varied in many ways. Such variations arenot to be regarded as a departure from the spirit and scope of thedisclosures and all such modifications are intended to be includedwithin the scope of the following claims.

What is claimed is:
 1. A method of clarifying a water system comprising:contacting a water system with a water clarification composition togenerate a treated water system, wherein the water clarificationcomposition comprises a compound or its salt derived from an aza-MichaelAddition Reaction between a polyamine and an activated olefin having anionic group according to one of the following formula

wherein: X is NH or O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2′) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; m is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H, —PO₃H,—OSO₃H, —OPO₃H, or a salt thereof; and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2, 3, or more positive charges or anioniccompound having 2, 3, or more negative charges.
 2. The method accordingto claim 1, wherein the polyamine is a linear, branched, or dendrimerpolyamine with a general formula of NH₂—[R^(10′)]_(n)—NH₂,(RNH)_(n)—RNH₂, H₂N—(RNH)_(n)—RNH₂, or H₂N—(RN(R′))_(n)—RNH₂, whereinR^(10′) is a linear or branched, unsubstituted or substituted C₂-C₁₀alkylene group, or combination thereof; R is —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted orsubstituted C₄-C₁₀ alkylene group, or combination thereof; R′ is —CH₂—,—CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstitutedor substituted C₄-C₁₀ alkyl group, RNH₂, RNHRNH₂, or RN(RNH₂)₂; and ncan be from 2 to 1,000,000.
 3. The method according to claim 1, whereinthe polyamine is an unmodified polyamine, and/or wherein the polyamineis a linear, branched, or dendrimer polyethyleneimine.
 4. The methodaccording to claim 3, wherein the polyamine comprises: only primary andsecondary amine groups; only primary, secondary, and tertiary aminegroups; or only primary and tertiary amine groups.
 5. The methodaccording to claim 1, wherein the polyamine has an average molecularweight (M_(w)) of from about 60 to about 2,000,000 Da, or from about 60to about 5,000 Da.
 6. The compound according to claim 1, wherein thepolyamine is a diamine or a triamine having an average molecular weight(M_(w)) of from about 60 to about 1,300.
 7. The method according toclaim 1, wherein the compound is of single molecule, a mixture of atleast two multiple charged cationic compounds, a mixture of at least twomultiple charged cationic derived from the same polyamine and theactivated olefin having a cationic group, a mixture of at least twomultiple charged anionic compounds, a mixture of at least two multiplecharged anionic compounds derived from the same polyamine and theactivated olefin having an anionic group, a mixture of at least twomultiple charged cationic or anionic compounds derived from differentpolyamines and the same activated olefin, or a mixture of at least twomultiple charged cationic or anionic compounds derived from differentpolyamines and different activated olefins.
 8. The method according toclaim 1, wherein the compound has an average molecular weight (M_(w)) offrom about 100 to about 2,000,000 Da, and is soluble in water.
 9. Themethod according to claim 1, wherein X is NH or O; R² is H or CH₃; Y is—NR₄R₅R₆ ⁽⁺⁾ is —NR⁴R⁵R⁶⁽⁺⁾ and R⁴, R⁵, and R⁶ are independently CH₃, Yis NR₄R₅R₆ ⁽⁺⁾ and R⁴ and R⁵ are independently CH₃, and R⁶ is a C₆-C₁₂aromatic alkyl, NR₄R₅R₆ ⁽⁺⁾ and R⁴ and R⁵ are independently CH₃, and R⁶is —CH₂—C₆H₆, or Y is NR₄R₅R₆ ⁽⁺⁾ and the counter ion for Y is chloride,bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide,dihydrogen phosphate, dihydrogen phosphite, formate, hydrogen carbonate,hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite,thiocyanate, or a combination thereof; Y′ is —COOH or salt thereof,—SO₃H or salt thereof, or —PO₃H or salt thereof; and R³ is CH₂,—CH₂CH₂—, —CH₂CH₂CH₂— or —C(CH₃)₂—, an unsubstituted, linear, andsaturated C₁-C₂₀ alkylene group, an unsubstituted, linear, andunsaturated C₁-C₂₀ alkylene group, a linear C₈-C₁₈ alkyl, alkenyl, oralkynyl group, or a branched C₈-C₂₀ alkyl, alkenyl, or alkynyl group.10. The method according to claim 1, wherein the compound is a mixturederived from (3-Acrylamidopropyl)trimethylammonium chloride (APTAC) or[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC). 11.The method according to claim 1, wherein the activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-timethylethan-1-aminium methylsulfate (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethanaminiumchloride (DMAEA-MSQ).
 12. The method according to claim 1, wherein theactivated olefin is an acrylic acid, methacrylic acid,2-acrylamido-2-methylpropane sulfonic acid (AMPS), itaconic acid, maleicacid, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, vinylsulfonic acid,vinylphosphonic acid, or mixture thereof.
 13. The compound according toclaim 1, wherein the multiple charged cationic or anionic compound isthe product mixture of: a linear polyethyleneimine and(3-Acrylamidopropyl)trimethylammonium chloride (APTAC) or[3-(Methacryloylamino)propyl]trimethylammonium chloride (MAPTAC); or abranched polyethyleneimine and (3-Acrylamidopropyl)trimethylammoniumchloride (APTAC) or [3-(Methacryloylamino)propyl]trimethylammoniumchloride (MAPTAC).
 14. The method according to claim 1, wherein thecompound is

wherein n=0-1000;


15. The method according to claim 1, wherein the compound is derivedfrom: a polyethyleneimine and (3-Acrylamidopropyl)trimethylammoniumchloride (APTAC), wherein the polyethyleneimine is a linear PEI and hasan average molecular weight (M_(w)) of about 5,000; a polyethyleneimineand (3-Acrylamidopropyl)trimethylammonium chloride (APTAC), wherein thepolyethyleneimine is a linear PEI and has au average molecular weight(M_(w)) of about 750,000; a polyethyleneimine and(3-Acrylamidopropyl)trimethylammonium chloride (APTAC), wherein thepolyethyleneimine is a branched PEI and has an average molecular weight(M_(w)) of about 25,000; or a diethylenetriamine and(3-Acrylamidopropyl)trimethylammonium chloride (APTAC).
 16. The methodaccording to claim 1, wherein the waste water source comprisesoil-in-water emulsion, and is an oily waste water from food and beverageprocess or water system used in oil refinery industry.
 17. The methodaccording to claim 1, wherein the clarification composition furthercomprises a carrier that is water, an alcohol, an alkylene glycol, analkyleneglycol alkyl ether, or a combination thereof.
 18. The methodaccording to claim 1, wherein the water clarification compositioncomprises from about 0.1 wt-% to about 90 wt-% of the multiple chargedcationic or anionic compound or its salt, and wherein the compositionfurther comprises one or more additional water clarification compositionagents, wherein the additional water clarification composition agent isa surfactant, acid, alkalinity source, additional coagulant/flocculantagent, biocide, or mixture thereof.
 19. The method according to claim 1,wherein the multiple charged cationic or anionic compound has aconcentration of from about 0.5 ppm to about 100 ppm in the treatedwater system after the water clarification composition is applied to thewater system.
 20. The method according to claim 1, wherein the methodfurther comprises contacting the water system with an additionalcoagulant/flocculant agent, wherein the additional coagulant/flocculantagent is another polymeric cationic, anionic, nonionic, or inorganiccoagulant/flocculant agent.
 21. The method according to claim 20,wherein the additional coagulant/flocculant agent is aluminum sulfate,aluminum chloride, ferric sulfate, ferric chloride, a mixture thereof.22. The method according to claim 20, wherein the additionalcoagulant/flocculant agent is: a high molecular weight polymericnonionic, anionic or cationic coagulant/flocculant agent and wherein thehigh molecular weight polymeric cationic coagulant/flocculant agent hasan average molecular weight (M_(w)) of from 100,000 to 2,000,000 Da, andwherein the high molecular weight polymeric cationiccoagulant/flocculant agent has net charges of from 10 to 1,000; or is alow molecular weight polymeric nonionic, anionic or cationiccoagulant/flocculant agent and wherein the low molecular weightpolymeric cationic coagulant/flocculant agent has an average molecularweight (M_(w)) of from 10,000 to 100,000 Da, and wherein the lowmolecular weight polymeric cationic coagulant/flocculant agent has netcharges of from 10 to 1,000.
 23. The method according to claim 1,wherein the method further comprises separating oil or solid from waterin the treated water system through filtration, settling, desalting,electrochemical techniques, centrifugation, flotation, or a combinationthereof.
 24. The method according to claim 1, wherein the waterclarification composition reduces turbidity of the water system.
 25. Awater clarification composition comprising: a compound or its salt andone or more water clarification composition agents, wherein the compoundis derived from an aza-Michael Addition Reaction between a polyamine andan activated olefin having an ionic group according to the followingformula

wherein: X is NH or O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; R^(2.) is H, CH₃, oran unsubstituted or substituted, linear or branched C₁-C₁₀ alkyl,alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or —(CH₂)_(m)—Y′; m is aninteger of 2 to 4; R³ is absent or an unsubstituted, linear or branchedC₁-C₃₀ alkylene group; Y is NR₄R₅R₆ ⁽⁺⁾; Y′ is —COOH, —SO₃H, —PO₃H,—OSO₃H, —OPO₃H, or a salt thereof, and R⁴, R⁵, and R⁶ are independentlya C₁-C₁₀ alkyl group; wherein the compound is a multiple chargedcationic compound having 2 or more positive charges or anionic compoundhaving 3 or more negative charges and wherein the water clarificationcomposition reduces turbidity of the water system.